Fungicidal compositions

ABSTRACT

A composition suitable for control of diseases caused by phytopathogens comprising (A) a compound of formula I 
                         
wherein R 1  is difluoromethyl or trifluoromethyl and X is chloro, fluoro or bromo; and (B) at least one compound selected from compounds known for their fungicidal activity; and a method of controlling diseases on useful plants, especially rust diseases on soybean plants.

This application is a divisional of U.S. patent application Ser. No.12/597,221 filed Mar. 10, 2010, which was a 371 of InternationalApplication No. PCT/EP2008/003279 filed Apr. 23, 2008, which claimspriority to EP 07008370.4 filed Apr. 25, 2007, the contents of which areall incorporated herein by reference.

The present invention relates to novel fungicidal compositions suitablefor control of diseases caused by phytopathogens, especiallyphytopathogenic fungi and to a method of controlling diseases on usefulplants, especially rust diseases on soybean plants.

It is known from WO 04/35589 and WO 06/37632 that certain tricyclicamine derivatives and mixtures comprising said amine derivatives havebiological activity against phytopathogenic fungi. On the other handvarious fungicidal compounds of different chemical classes are widelyknown as plant fungicides for application in various crops of cultivatedplants. However, crop tolerance and activity against phytopathogenicplant fungi do not always satisfy the needs of agricultural practice inmany incidents and aspects. For example, in the past in the mostimportant regions for soybean cultures no economically significantphytopathogens were known. However, recently there has been an increasein severe rust infections of soybean crops in South America by theharmful fungus Phakopsora pachyrhizi resulting in considerable yieldlosses. Most customary fungicides are unsuitable for controlling rust insoybeans or their action against Phakopsora pachyrhizi isunsatisfactory.

Out of the above-mentioned needs of agricultural practice for increasedcrop tolerance and/or increased activity against phytopathogenic fungi,such as Phakopsora pachyrhizi, there is therefore proposed in accordancewith the present invention a novel composition suitable for control ofdiseases caused by phytopathogens comprising

a composition suitable for control of diseases caused by phytopathogenscomprising

(A) a compound of formula I

wherein R₁ is difluoromethyl or trifluoromethyl and X is chloro, fluoroor bromo; and

(B) at least one compound selected from the group consisting of

(B1) a strobilurin fungicide,

(B2) an azole fungicide,

(B3) a morpholine fungicide,

(B4) an anilinopyrimidine fungicide,

(B5) a fungicide selected from the group consisting of

anilazine, arsenates, benalaxyl, benalaxyl-M, benodanil, benomyl,benthiavalicarb, benthiavalicarb-isopropyl, biphenyl, bitertanol,blasticidin-S, bordeaux mixture, boscalid, bupirimate, cadmium chloride,captafol, captan, carbendazim, carbon disulfide, carboxin, carpropamid,cedar leaf oil, chinomethionat, chlorine, chloroneb, chlorothalonil,chlozolinate, cinnamaldehyde, copper, copper ammoniumcarbonate, copperhydroxide, copper octanoate, copper oleate, copper sulphate, cyazofamid,cycloheximide, cymoxanil, dichlofluanid, dichlone, dichloropropene,diclocymet, diclomezine, dicloran, diethofencarb, diflumetorim,dimethirimol, dimethomorph, dinocap, dithianon, dodine, edifenphos,ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone, fenaminosulf,fenamiphos, fenarimol, fenfuram, fenhexamid, fenoxanil, fenpiclonil,fentin acetate, fentin chloride, fentin hydroxide, ferbam, ferimzone,fluazinam, fludioxonil, flusulfamide, flusulfamide, flutolanil, folpet,formaldehyde, fosetyl-aluminium, fthalide, fuberidazole, furalaxyl,furametpyr, flyodin, fuazatine, hexachlorobenzene, hymexazole,iminoctadine, iodocarb, iprobenfos, iprodione, iprovalicarb,isoprothiolane, kasugamycin, mancozeb, maneb, manganousdimethyldithiocarbamate, mefenoxam, mepronil, mercuric chloride,mercury, metalaxyl, methasulfocarb, metiram, metrafenone, nabam, neemoil (hydrophobic extract), nuarimol, octhilinone, ofurace, oxadixyl,oxine copper, oxolinic acid, oxycarboxin, oxytetracycline,paclobutrazole, paraffin oil, paraformaldehyde, pencycuron,pentachloronitrobenzene, pentachlorophenol, penthiopyrad, perfurazoate,phosphoric acid, polyoxin, polyoxin D zinc salt, potassium bicarbonate,probenazole, procymidone, propamocarb, propineb, proquinazid,prothiocarb, pyrazophos, pyrifenox, pyroquilon, quinoxyfen, quintozene,silthiofam, sodium bicarbonate, sodium diacetate, sodium propionate,streptomycin, sulphur, TCMTB, tecloftalam, tecnazene, thiabendazole,thifluzamide, thiophanate, thiophanate-methyl, thiram, tolclofos-methyl,tolyfluanid, triazoxide, trichoderma harzianum, tricyclazole, triforine,triphenyltin hydroxide, validamycin, vinclozolin, zineb, ziram,zoxamide, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenylbenzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide,4-chlorophenyl phenyl sulfone,

a compound of formula B-5.1

a compound of formula B-5.2

a compound of formula B-5.3

a compound of formula B-5.4

a compound of formula B-5.5

a compound of formula B-5.6

a compound of formula B-5.7

3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(2-bicyclopropyl-2-yl-phenyl)-amide (compound B-5.8),3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(9-isopropyp-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide(compound B-5.9), 1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxylic acid[2-(1,3-dimethylbutyl)phenyl]-amide (compound B-5.10),3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(3′,4′-dichloro-5-fluoro-1,1′-biphenyl-2-yl)-amide (compound B-5.11),N-{2-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]ethyl}-2-(trifluoromethyl)benzamid(compound B-5.12), 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylicacid N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-amide (compound B-5.13),3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acidN-[2-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-amide (compound B-5.14),3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acidN-[2-(2-chloro-1,1,2-trifluoroethoxy)phenyl]-amide (compound B-5.15),3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acidN-(4′-trifluoromethyl-biphen-2-yl)-amide (compound B-5.16),3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acidN-(2′-trifluoromethyl-biphen-2-yl)-amide (compound B-5.17) and3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acidN-(2′-trifluoromethyl-biphen-2-yl)-amide (compound B-5.18); (B6) aplant-bioregulator selected from the group consisting of

acibenzolar-S-methyl, chlormequat chloride, ethephon, mepiquat chlorideand trinexapc-ethyl;

(B7) an insecticide selected from the group consisting of

abamectin, clothianidin, emamectin benzoate, imidacloprid, tefluthrin,thiamethoxam,

and a compound of formula IV

wherein X is a bivalent group selected from

wherein

a) R₁ is cyclopropyl substituted by cyclopropyl at the 1-position, R₂ isbromine, R₃ is methyl, R₄ is CN and X is X₁;

b) R₁ is methyl substituted by cyclopropyl, R₂ is CF₃, R₃ is methyl, R₄is Cl and X is X₁;

c) R₁ is cyclopropyl substituted by cyclopropyl at the 1-position, R₂ isCF₃, R₃ is methyl, R₄ is Cl and X is X₁;

d) R₁ is cyclopropyl substituted by cyclopropyl at the 1-position, R₂ isCF₃, R₃ is methyl, R₄ is CN and X is X₁;

e) R₁ is cyclopropyl substituted by cyclopropyl at the 1-position, R₂ isOCH₂CF₃, R₃ is methyl, R₄ is ON and X is X₁;

f) R₁ is isopropyl, R₂ is methoxy; R₃ is methyl, R₄ is hydrogen and X isX₈;

g) R₁ is isopropyl, R₂ is trifluoromethyl, R₃ is chlorine, R₄ ishydrogen and X is X₈;

h) R₁ is isopropyl, R₂ is trifluoromethyl, R₃ is methyl, R₄ is hydrogenand X is X₈;

i) R₁ is methyl, R₂ is bromine, R₃ is methyl, R₄ is CN and X is X₁;

j) R₁ is methyl, R₂ is bromine, R₃ is methyl, R₄ is Cl and X is X₁; and(B8) glyphosate, a compound of formula V

fomesafen, and (B9) a racemic compound of formula VIa (syn)

wherein Ra₇ is trifluoromethyl or difluoromethyl; a racemic mixture offormula VIb (anti)

wherein Ra₇ is trifluoromethyl or difluoromethyl; a compound of formulaVIc

which is an epimeric mixture of racemic compounds of formulae F-10 (syn)and F-11 (anti), wherein the ratio from racemic compounds of formulaF-10 (syn) to racemic compounds of formula F-11 (anti) is from 1000:1 to1:1000 and wherein Ra₇ is trifluoromethyl or difluoromethyl.

Preferred compositions comprising (A) a compound of formula I

wherein R₁ is difluoromethyl or trifluoromethyl and X is chloro, fluoroor bromo; and

(B) a compound selected from the group consisting of

(B1) a strobilurin fungicide, (B2) an azole fungicide, (B3) a morpholinefungicide, (B4) an anilinopyrimidine fungicide, (B5) a fungicideselected from the group consisting of anilazine (878), arsenates,benalaxyl (56), benalaxyl-M, benodanil (896), benomyl (62),benthiavalicarb, benthiavalicarb-isopropyl (68), biphenyl (81),bitertanol (84), blasticidin-S (85), bordeaux mixture (87), boscalid(88), bupirimate (98), cadmium chloride, captafol (113), captan (114),carbendazim (116), carbon disulfide (945), carboxin (120), carpropamid(122), cedar leaf oil, chinomethionat (126), chlorine, chloroneb (139),chlorothalonil (142), chlozolinate (149), cinnamaldehyde, copper, copperammoniumcarbonate, copper hydroxide (169), copper octanoate (170),copper oleate, copper sulphate (87), cyazofamid (185), cycloheximide(1022), cymoxanil (200), dichlofluanid (230), dichlone (1052),dichloropropene (233), diclocymet (237), diclomezine (239), dicloran(240), diethofencarb (245), diflumetorim (253), dimethirimol (1082),dimethomorph (263), dinocap (270), dithianon (279), dodine (289),edifenphos (290), ethaboxam (304), ethirimol (1133), etridiazole (321),famoxadone (322), fenamidone (325), fenaminosulf (1144), fenamiphos(326), fenarimol (327), fenfuram (333), fenhexamid (334), fenoxanil(338), fenpiclonil (341), fentin acetate (347), fentin chloride, fentinhydroxide (347), ferbam (350), ferimzone (351), fluazinam (363),fludioxonil (368), flusulfamide (394), flutolanil (396), folpet (400),formaldehyde (404), fosetyl-aluminium (407), fthalide (643),fuberidazole (419), furalaxyl (410), furametpyr (411), flyodin (1205),fuazatine (422), hexachlorobenzene (434), hymexazole, iminoctadine(459), iodocarb (3-Iodo-2-propynyl butyl carbamate), iprobenfos (IBP)(469), iprodione (470), iprovalicarb (471), isoprothiolane (474),kasugamycin (483), mancozeb (496), maneb (497), manganousdimethyldithiocarbamate, mefenoxam (Metalaxyl-M) (517), mepronil (510),mercuric chloride (511), mercury, metalaxyl (516), methasulfocarb (528),metiram (546), metrafenone, nabam (566), neem oil (hydrophobic extract),nuarimol (587), octhilinone (590), ofurace (592), oxadixyl (601), oxinecopper (605), oxolinic acid (606), oxycarboxin (608), oxytetracycline(611), paclobutrazole (612), paraffin oil (628), paraformaldehyde,pencycuron (620), pentachloronitrobenzene (716), pentachlorophenol(623), penthiopyrad, perfurazoate, phosphoric acid, polyoxin (654),polyoxin D zinc salt (654), potassium bicarbonate, probenazole (658),procymidone (660), propamocarb (668), propineb (676), proquinazid (682),prothiocarb (1361), pyrazophos (693), pyrifenox (703), pyroquilon (710),quinoxyfen (715), quintozene (PCNB) (716), silthiofam (729), sodiumbicarbonate, sodium diacetate, sodium propionate, streptomycin (744),sulphur (754), TCMTB, tecloftalam, tecnazene (TCNB) (767), thiabendazole(790), thifluzamide (796), thiophanate (1435), thiophanate-methyl (802),thiram (804), tolclofos-methyl (808), tolylfluanid (810), triazoxide(821), trichoderma harzianum (825), tricyclazole (828), triforine (838),triphenyltin hydroxide (347), validamycin (846), vinclozolin (849),zineb (855), ziram (856), zoxamide (857),1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC-Name) (910),2,4-dichlorophenyl benzenesulfonate (IUPAC-/Chemical Abstracts-Name)(1059), 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC-Name) (1295),4-chlorophenyl phenyl sulfone (IUPAC-Name) (981),

a compound of formula B-5.1

a compound of formula B-5.2

a compound of formula B-5.3

a compound of formula B-5.4

a compound of formula B-5.5

a compound of formula B-5.6

a compound of formula B-5.7

3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(2-bicyclopropyl-2-yl-phenyl)-amide (compound B-5.8),3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(9-isopropyp-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide(compound B-5.9), 1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxylic acid[2-(1,3-dimethylbutyl)phenyl]-amide (compound B-5.10),3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(3′,4′-dichloro-5-fluoro-1,1′-biphenyl-2-yl)-amide (compound B-5.11),N-{2-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]ethyl}-2-(trifluoromethyl)benzamid(compound B-5.12), 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylicacid N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-amide (compound B-5.13),3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acidN-[2-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-amide (compound B-5.14),3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acidN-[2-(2-chloro-1,1,2-trifluoroethoxy)phenyl]-amide (compound B-5.15),3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acidN-(4′-trifluoromethyl-biphen-2-yl)-amide (compound B-5.16),3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acidN-(2′-trifluoromethyl-biphen-2-yl)-amide (compound B-5.17) and3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acidN-(2′-trifluoromethyl-biphen-2-yl)-amide (compound B-5.18); (B6) aplant-bioregulator selected from the group consisting ofacibenzolar-5-methyl (6), chlormequat chloride (137), ethephon (307),mepiquat chloride (509) and trinexapc-ethyl (841);

(B7) an insecticide selected from the group consisting of

abamectin (1), clothianidin (165), emamectin benzoate (291),imidacloprid (458), tefluthrin (769), thiamethoxam (792), a compound offormula B-7.1

and a compound of formula B-7.2;

and (B8) glyphosate (419).

It has been found that the use of component (B) in combination withcomponent (A) surprisingly and substantially enhance the effectivenessof the latter against fungi, and vice versa. Additionally, the method ofthe invention is effective against a wider spectrum of such fungi thatcan be combated with the active ingredients of this method, when usedsolely.

A further aspect of the present invention is a method of controllingdiseases on useful plants or on propagation material thereof caused byphytopathogens, which comprises applying to the useful plants, the locusthereof or propagation material thereof a composition according to theinvention. Preferred is a method, which comprises applying to the usefulplants or to the locus thereof a composition according to the invention,more preferably to the useful plants. Further preferred is a method,which comprises applying to the propagation material of the usefulplants a composition according to the invention.

The compounds of formula I occur in two different stereoisomers, whichare described as the single enantiomers of formulae I_(I) and I_(II):

The invention covers all such stereoisomers and mixtures thereof in anyratio. According to the invention “racemic compound of formula (I)”means a racemic mixture of compounds of formula I_(I) and I_(II).

A preferred embodiment of the invention is represented by thosecompositions which comprise as component A) a compound of formula (I),wherein R₁ is difluoromethyl. Further preferred compounds of formula (I)are:

-   3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid    (9-dichloromethylidene-benzonorbornene-5-yl)amide (compound A-1.1);    3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid    (9-difluoromethylidene-benzonorbornene-5-yl)amide (compound A-1.2);    and-   3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid    (9-dibromomethylidene-benzonorbornene-5-yl)amide (compound A-1.3).

The designation of substituent X as chloro, fluoro or bromo means thatboth substituents X have the same meanings.

A preferred embodiment of the invention is represented by thosecompositions which comprise as component A) a compound of formula (I),wherein R₁ is trifluoromethyl. Further preferred compounds of formula(I) are:

-   1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid    (9-dichloromethylidene-benzonorbornene-5-yl)amide (compound A-1.4);-   1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid    (9-difluoromethylidene-benzonorbornene-5-yl)amide (compound A-1.5);    and-   1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid    (9-dibromomethylidene-benzonorbornene-5-yl)amide (compound A-1.6).

A further preferred embodiment of the invention is represented by thosecompositions which comprise as component B) a compound selected fromazoxystrobin, picoxystrobin, fludioxonil, fenpropidin, difenoconazole,cyprodinil, mandipropamid, chlorothalonil, cyproconazole, epoxiconazole,propiconazole and epoxiconazole.

Especially preferred compositions according to the invention comprise ascomponent (A) a compound selected from3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(9-dichloromethylidene-benzonorbornene-5-yl)amide (compound A-1.1) and3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(9-difluoromethylidene-benzonorbornene-5-yl)amide (compound A-1.2), andas component (B) a compound selected from azoxystrobin, picoxystrobin,bixafen, fludioxonil, fenpropidin, fenpropimorph, fluopyram,difenoconazole, tebuconazole, ipconazole, cyprodinil, mandipropamid,chlorothalonil, cyproconazole, prothioconazole, propiconazole andepoxiconazole.

Further especially preferred compositions according to the inventioncomprise as component (A) the compound3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(9-dichloromethylidene-benzonorbornene-5-yl)amide (compound A-1.1) andas component (B) a compound selected from azoxystrobin, picoxystrobin,bixafen, fludioxonil, fenpropidin, difenoconazole, cyprodinil,mandipropamid, chlorothalonil, propiconazole, cyproconazole andepoxiconazole.

Further especially preferred compositions according to the inventioncomprise as component (A) the compound3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(9-difluoromethylidene-benzonorbornene-5-yl)amide (compound A-1.2) andas component (B) a compound selected from azoxystrobin, picoxystrobin,fludioxonil, fenpropidin, fenpropimorph, fluopyram, difenoconazole,ipconazole, prothioconazole, tebuconazole, cyprodinil, chlorothalonil,epoxiconazole, propiconazole, cyproconazole, and epoxiconazole.

The compounds of formula (I) may be prepared as described below withreference to reaction Schemes 1 to 3.

As shown in Scheme 1, a compound of formula (I), where R₁ and X are asdefined above, may be synthesized by reacting a compound of formula(II), R₁ is as defined above and R′ is C₁₋₅ alkyl, with an aniline offormula (III), where X is as defined above, in the presence of NaN(TMS)₂at −10° C. to ambient temperature, preferably in dry THF, as describedby J. Wang et al. Synlett, 2001, 1485.

Alternatively, as shown in Scheme 2, a compound of formula (I), whereHet is as defined in scheme 1, R₁ and X are as defined above, may beprepared by reacting a compound of formula (II′), where Het is asdefined above, with an aniline of formula (III), where X is as definedabove, in the presence of an activating agent, such as BOP-CI(bis-(2-oxo-3-oxazolidinyl)-phosphinic acid), and two equivalents of abase, such as triethylamine, in a solvent, such as dichloromethane (asdescribed, for example, by J. Cabré et al, Synthesis 1984, 413) or byreacting a compound of formula (II″), where Het is as defined above andQ is chloro, fluoro or bromo, with an aniline of formula (III), where Xis as defined above, in the presence of one equivalent of a base, suchas triethylamine or sodium or potassium carbonate or bicarbonate, in asolvent, such as dichloromethane, ethyl acetate orN,N-dimethylformamide, preferably at −10 to 30° C. The compound offormula (II″) is obtained from a compound of formula (II′) by treatmentwith a halogenating agent such as thionyl chloride, thionyl bromide,oxalyl chloride, phosgene, SF₄/HF, DAST ((diethylamino)sulphurtrifluoride), or Deoxo-Fluor® ([bis(2-methoxyethyl)amino]sulphurtrifluoride) in a solvent such as toluene, dichloromethane oracetonitrile.

The compounds (II) and (II′) are generally known compounds and may beprepared as described in the chemical literature or obtained fromcommercial sources. The compound (III) is a novel compound and may beprepared as described with reference to Scheme 3.

As shown Scheme 3, the compound of formula (III) may be prepared by aBechamp reduction or by other established methods, for example, byselective catalytic hydrogenation, of the nitro-compounds (E), (F) and(G).

The 9-dihalomethylidene-5-nitro-benzonorbornenes (E), where X is chloro,bromo or fluoro, may be obtained by the Wittig olefination of theketones (D) with in situ generated dihalomethylidene phosphoranesR′″₃P═C(R⁴)R⁵, where R′″ is triphenyl, tri C₁₋₄ alkyl ortridimethylamine and X is halo, according to or by analogy with theprocedures described by H-D. Martin et al, Chem. Ber. 118, 2514 (1985),S. Hayashi et al, Chem. Lett. 1979, 983, or M. Suda, TetrahedronLetters, 22, 1421 (1981).

Compounds of formula (I) may be obtained as described in examples H1 toH7.

EXAMPLE 1

This Example illustrates the preparation of1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid(9-dichloromethylidene-benzonorbornene-5-yl)amide (compound A-1.4):

9-Dichloromethylene-5-amino-benzonorbornene (175 mg, 0.729 mmol,prepared as described in Example 6) in dichloromethane (10 ml) wasreacted with 1-methyl-3-trifluoromethyl-1H-pyrazole-carboxylic acid (170mg, 0.874 mmol, 1.2 eq.) in the presence ofbis-(2-oxo-3-oxazolidinyl)-phosphinic acid chloride (278 mg, 1.09 mmol,1.5 eq.) and triethylamine (184 mg, 1.821 mmol, 2.5 eq.) at ambienttemperature under stirring for 23 hours. The reaction mixture wasextracted with saturated sodium bicarbonate solution and saturatedbrine, dried over Na₂SO₄ and purified on silica gel in ethylacetate-hexane-(1:1). 210 mg (69% of theory) of1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid(9-dichloromethylidene-benzonorbornene-5-yl)amide (compound A-1.4, m.p.179-181° C.) was obtained.

EXAMPLE 2

This Example illustrates the preparation of9-(3-pentylidene)-5-nitro-benzonorbornadiene:

To a well stirred solution of isopentylnitrite (2.31 ml, 1.3 eq.) indimethoxyethane (50 ml) at 58° C. a mixture of 6-nitroanthranilic acid(2.76 g, 1 eq.) and 6,6-diethylfulvene (6.45 g of 79% purity, 2.5 eq.)dissolved in 25 ml dimethoxyethane was added dropwise within 8 minuteswhilst the temperature rose to 67° C. After 30 minutes the dark reactionmixture was evaporated and purified on silica gel in hexane-ethylacetate-(20:1) to give 3.02 g (78%) of the desired product as an oilthat solidified at room temperature (m.p. 60-61° C.).

EXAMPLE 3

This Example illustrates the preparation of9-(3-pentylidene)-5-nitro-benzonorbornene:

9-(3-pentylidene)-5-nitro-benzonorbornadiene (7.97 g prepared asdescribed in Example 2) in THF (70 ml) was hydrogenated at 20° C. in thepresence of Rh(PPh₃)₃Cl (Wilkinson's catalyst; 0.8 g). The reactionceased after uptake of one equivalent of hydrogen.

Evaporation and filtration of the crude on silica gel in ethylacetate-hexane-(100:2) gave the desired product as an oil (7.90 g) thatsolidified on standing at room temperature (m.p. 69-56° C.).

EXAMPLE 4

This Example illustrates the preparation of9-Oxo-5-nitro-benzonorbornene

9-(3-pentylidene)-5-nitro-benzonorbornene (7.0 g, 27.2 mmol; prepared asdescribed in Example 3) dissolved in dichloromethane (300 ml) andmethanol (5 ml) was ozonized (2.8 l O₂/min, 100 Watt, corresponding to9.7 g O₃/h) at −70° C. until a persistent blue colour was observed(after approximately 15 minutes). The reaction mixture was flushed withnitrogen gas. Triphenylphosphine (8.4 g, 32.03 mmol, 1.18 eq.) was addedand the temperature was allowed to warm up to 20-25° C. Afterevaporation of the solvent the residue was purified on silica gel inhexane-EtOAc-3:1 to give 5.2 g of Compound 36.01 (m.p. 112-114° C.).

EXAMPLE 5

This Example illustrates the preparation of9-difluoromethylidene-5-nitro-benzonorbornene

To a solution of dibromodifluoromethane (6.30 g, 30 mmol) at 00° C. inTHF (50 ml) was added tris-(dimethylamino)-phosphane (10.1 g at 97%,equivalent to 11.2 ml, 60 mmol) in THF (30 ml) within 20 minutes. To theresulting suspension, after stirring for 1 hour at room temperature, wasadded dropwise a solution of 9-oxo-5-nitro-benzonorbornene (6.10 g, 30mmol; prepared as described in Example 4) in THF (20 ml) within 25minutes followed by stirring for 21 hours. The suspension was pouredonto ice-water and extracted with ethyl acetate. Purification on silicagel in ethyl acetate-hexane-(1:4) yielded 4.675 g of9-difluoromethylidene-5-nitro-benzonorbornene (m.p. 99-101° C.).

EXAMPLE 6

This Example illustrates the preparation of9-Dichloromethylidene-5-nitro-benzonorbornene

Dry carbon tetrachloride (5.9 g, 33 mmol) was reacted withtriphenylphosphine (14.46 g, 55.1 mmol) in dichloromethane (30 ml) atroom temperature for 1 hour. 9-Oxo-5-nitro-benzonorbornene (5.60 g,27.56 mmol; prepared as described in Example 4) in dichloromethane (10ml) was added dropwise and stirred for 20 hours at room temperature.After aqueous work-up (ice-water) and extraction with dichloromethane,the crude product was purified on silica gel in ethylacetate-hexane-(1:4) to obtain of the desired9-Dichloromethylidene-5-nitro-benzonorbornene (1.83 g; m.p. 136-137°C.). Some starting material (4.06 g) was recovered.

EXAMPLE 7

This Example illustrates the preparation of9-Dibromomethylidene-5-nitro-benzonorbornene

Carbon tetrabromide (4.66 g at 98%, 13.8 mmol) was reacted understirring with triphenylphosphine (7.23 g, 27.6 mmol) in dichloromethane(50 ml) for 50 minutes at room temperature.9-Oxo-5-nitro-benzonorbornene (2.8 g, 13.8 mmol; prepared as describedin Example 4) in dichloromethane (10 ml) was added dropwise and stirredover night at room temperature. Aqueous work-up (ice-water) andextraction with dichloromethane followed by column chromatography (ethylacetate-hexane-(1:9) of the crude product yielded the desired product9-Dibromomethylidene-5-nitro-benzonorbornene (2.1 g; m.p. 153-155° C.).

TABLE 1 Table 1 shows melting point and NMR data, all with CDCl₃ as thesolvent, unless otherwise stated, for compounds of formula (I). Compundm.p (° C.) ¹H-NMR proton shifts δ (ppm) (CDCl₃) A-1.1 179-181 8.06 (s,1H), 7.69 (d overlapped by brd signal, exchangeable with D₂O, 2H), 7.18(t, 1H), 7.06 (d, 1H), 4.00 (s, 3H), 3.96 (m, 2H), 2.12 (m, 2H), 1.51(m, 1H), 1.39 (m, 1H). A-1.2 137-143 8.06 (s, 1H), 7.68 (brd,exchangeable with D₂O, 1H), 7.67 (d, 1H), 7.14 (d, 1H), 4.00 (s, 3H),3.94 (m, 2H), 2.06 (m, 2H), 1.48 (m, 1H), 1.36 (m. 1H). A-1.3 198-2008.06 (s, 1H), 7.71 (d, 1H), 7.68 (brd, exchangeable with D₂O, 1H), 7.18(t, 1H), 7.05 (d, 1H), 4.00 (s, 3H), 3.95 (m, 1H), 3.93 (m, 1H), 2.12(m, 2H), 1.50 (m, 1H), 1.38 (m, 1H). A-1.4 183-188 7.78 (d, 1H), 7.70(brd, exchangeable with D₂O, 1H), 7.39 (brd s, 1H), 7.16 (t, 1H), 7.01(d overlapped from brd s, 2H), 4.00 (m, 1H), 3.94 (m, 1H), 3.72 (s, 3H),2.10 (m, 2H), 1.51 (m, 1H), 1.38 (m, 1H). A-1.5 133-135 7.76 (d, 1H),7.70 (brd, exchangeable with D₂O, 1H), 7.39 (brd s, 1H), 7.13 (t, 1H),7.01 (brd s, 1H), 7.00 (d, 1H), 3.98 (m, 1H), 3.93 (m, 1H), 3.72 (s,3H), 2.04 (m, 2H), 1.49 (m, 1H), 1.36 (m, 1H). A-1.6 155-158 7.79 (d,1H), 7.70 (brd, exchangeable with D₂O, 1H), 7.39 (brd s, 1H), 7.17 (t,1H), 7.02 (d, 1H), 7.01 (brd s, 1H), 3.98 (m, 1H), 3.91 (m, 1H), 3.72(s, 3H), 2.11 (m, 2H), 1.50 (m, 1H), 1.39 (m, 1H). In the table,temperatures are given in degrees Celsius, “NMR” means nuclear magneticresonance spectrum and the following abbreviations are used: m.p. =melting point s = singlet d = doublet t = triplet m = multiplet THF =tetrahydrofuran b.p. = boiling point. br = broad dd = doublet ofdoublets q = quartet ppm = parts per million

The components (B) are known. Where the components (B) are included in“The Pesticide Manual” [The Pesticide Manual—A World Compendium;Thirteenth Edition; Editor: C. D. S. Tomlin; The British Crop ProtectionCouncil], they are described therein under the entry number given inround brackets hereinabove for the particular component (B); forexample, the compound “abamectin” is described under entry number (1).Most of the components (B) are referred to hereinabove by a so-called“common name”, the relevant “ISO common name” or another “common name”being used in individual cases. If the designation is not a “commonname”, the nature of the designation used instead is given in roundbrackets for the particular component (B); in that case, the IUPAC name,the IUPAC/Chemical Abstracts name, a “chemical name”, a “traditionalname”, a “compound name” or a “development code” is used or, if neitherone of those designations nor a “common name” is used, an “alternativename” is employed.

The following components B) are registered under a CAS-Reg. No.

aldimorph (CAS 91315-15-0); arsenates (CAS 1327-53-3); benalaxyl-M (CAS98243-83-5); benthiavalicarb (CAS 413615-35-7); cadmium chloride (CAS10108-64-2); cedar leaf oil (CAS 8007-20-3); chlorine (CAS 7782-50-5);cinnamaldehyde (CAS: 104-55-2); copper ammoniumcarbonate (CAS33113-08-5); copper oleate (CAS 1120-44-1); iodocarb (3-Iodo-2-propynylbutyl carbamate) (CAS 55406-53-6); hymexazole (CAS 10004-44-1);manganous dimethyldithiocarbamate (CAS 15339-36-3); mercury (CAS7487-94-7; 21908-53-2; 7546-30-7); metrafenone (CAS 220899-03-6); neemoil (hydrophobic extract) (CAS 8002-65-1); orysastrobin CAS248593-16-0); paraformaldehyde (CAS 30525-89-4); penthiopyrad (CAS183675-82-3); phosphoric acid (CAS 7664-38-2); potassium bicarbonate(CAS 298-14-6); sodium bicarbonate (CAS 144-55-8); sodium diacetate (CAS127-09-3); sodium propionate (CAS 137-40-6); TCMTB (CAS 21564-17-0); andtolyfluanid (CAS 731-27-1).

Compound B-1.1 (“enestrobin”) is described in EP-0-936-213; compoundB-3.1 (“flumorph”) in U.S. Pat. No. 6,020,332, CN-1-167-568,CN-1-155-977 and in EP-0-860-438; compound B-5.1 (“mandipropamid”) in WO01/87822; compound B-5.2 in WO 98/46607; compound B-5.3 (“fluopicolide”)in WO 99/42447; compound B-5.4 (“cyflufenamid”) in WO 96/19442; compoundB-5.5 in WO 99/14187; compound B-5.6 (“pyribencarb”) is registered underCAS-Reg. No. 325156-49-8; compound B-5.7 (“amisulbrom” or “ambromdole”)is registered under CAS-Reg. No. 348635-87-0; compound B-5.8(3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(2-bicyclopropyl-2-yl-phenyl)-amide) is described in WO 03/74491;compound B-5.9 (3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(9-isopropyp-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide) isdescribed in WO 04/35589 and in WO 06/37632; compound B-5.10(1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxylic acid[2-(1,3-dimethylbutyl)phenyl]-amide) is described in WO 03/10149;compound B-5.11 (3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(3′,4′-dichloro-5-fluoro-1,1′-biphenyl-2-yl)-amide; “bixafen”) isregistered under CAS-Reg. No.: 581809-46-3 and described in WO 03/70705;compound B-5.12(N-{2-[3-Chloro-5-(trifluoromethyl)pyridin-2-yl]ethyl}-2-(trifluoromethyl)benzamid;“fluopyram”) is registered under CAS-Reg. No: 658066-35-4 and describedin WO 04/16088; compounds B-5.13, B-5.14 and B-5.15 are described in WO07/17450; compounds B-5.16, B-5.17 and B-5.18 are described in WO06/120219; The compounds of formula IV are for example described in WO04/067528, WO 2005/085234, WO 2006/111341, WO 03/015519, WO 2007/020050,WO 2006/040113, and WO 2007/093402. The compound of formula V isdescribed in WO 01/94339. The compounds of formula VIa, VIb and VIc isdescribed in WO 04/35589 and in PCT/EP2005/010755. Fomesafen isregistered under the CAS-Reg. No. 72178-02-0.

Examples of especially suitable compounds as component (B) are compoundsselected from the following group P:

Group P: Especially Suitable Compounds as Component (B) in theCompositions According to the Invention:

a strobilurin fungicide selected from azoxystrobin (47), dimoxystrobin(226), fluoxastrobin (382), kresoxim-methyl (485), metominostrobin(551), orysastrobin, picoxystrobin (647), pyraclostrobin (690);trifloxystrobin (832), a compound of formula B-1.1

an azole fungicide selected from azaconazole (40), bromuconazole (96),cyproconazole (207), difenoconazole (247), diniconazole (267),diniconazole-M (267), epoxiconazole (298), fenbuconazole (329),fluquinconazole (385), flusilazole (393), flutriafol (397), hexaconazole(435), imazalil (449), imibenconazole (457), ipconazole (468),metconazole (525), myclobutanil (564), oxpoconazole (607), pefurazoate(618), penconazole (619), prochloraz (659), propiconazole (675),prothioconazole (685), simeconazole (731), tebuconazole (761),tetraconazole (778), triadimefon (814), triadimenol (815), triflumizole(834), triticonazole (842), diclobutrazol (1068), etaconazole (1129),furconazole (1198), furconazole-cis (1199) and quinconazole (1378);

a morpholine fungicide selected from aldimorph, dodemorph (288),fenpropimorph (344), tridemorph (830), fenpropidin (343), spiroxamine(740), piperalin (648) and a compound of formula B-3.1

an anilino-pyrimidine fungicide selected from cyprodinil (208),mepanipyrim (508) and pyrimethanil (705);

a fungicide selected from the group consisting of

anilazine (878), arsenates, benalaxyl (56), benalaxyl-M, benodanil(896), benomyl (62), benthiavalicarb, benthiavalicarb-isopropyl (68),biphenyl (81), bitertanol (84), blasticidin-S (85), bordeaux mixture(87), boscalid (88), bupirimate (98), cadmium chloride, captafol (113),captan (114), carbendazim (116), carbon disulfide (945), carboxin (120),carpropamid (122), cedar leaf oil, chinomethionat (126), chlorine,chloroneb (139), chlorothalonil (142), chlozolinate (149),cinnamaldehyde, copper, copper ammoniumcarbonate, copper hydroxide(169), copper octanoate (170), copper oleate, copper sulphate (87),cyazofamid (185), cycloheximide (1022), cymoxanil (200), dichlofluanid(230), dichlone (1052), dichloropropene (233), diclocymet (237),diclomezine (239), dicloran (240), diethofencarb (245), diflumetorim(253), dimethirimol (1082), dimethomorph (263), dinocap (270), dithianon(279), dodine (289), edifenphos (290), ethaboxam (304), ethirimol(1133), etridiazole (321), famoxadone (322), fenamidone (325),fenaminosulf (1144), fenamiphos (326), fenarimol (327), fenfuram (333),fenhexamid (334), fenoxanil (338), fenpiclonil (341), fentin acetate(347), fentin chloride, fentin hydroxide (347), ferbam (350), ferimzone(351), fluazinam (363), fludioxonil (368), flusulfamide (394),flutolanil (396), folpet (400), formaldehyde (404), fosetyl-aluminium(407), fthalide (643), fuberidazole (419), furalaxyl (410), furametpyr(411), flyodin (1205), fuazatine (422), hexachlorobenzene (434),hymexazole, iminoctadine (459), iodocarb (3-Iodo-2-propynyl butylcarbamate), iprobenfos (IBP) (469), iprodione (470), iprovalicarb (471),isoprothiolane (474), kasugamycin (483), mancozeb (496), maneb (497),manganous dimethyldithiocarbamate, mefenoxam (Metalaxyl-M) (517),mepronil (510), mercuric chloride (511), mercury, metalaxyl (516),methasulfocarb (528), metiram (546), metrafenone, nabam (566), neem oil(hydrophobic extract), nuarimol (587), octhilinone (590), ofurace (592),oxadixyl (601), oxine copper (605), oxolinic acid (606), oxycarboxin(608), oxytetracycline (611), paclobutrazole (612), paraffin oil (628),paraformaldehyde, pencycuron (620), pentachloronitrobenzene (716),pentachlorophenol (623), penthiopyrad, perfurazoate, phosphoric acid,polyoxin (654), polyoxin D zinc salt (654), potassium bicarbonate,probenazole (658), procymidone (660), propamocarb (668), propineb (676),proquinazid (682), prothiocarb (1361), pyrazophos (693), pyrifenox(703), pyroquilon (710), quinoxyfen (715), quintozene (PCNB) (716),silthiofam (729), sodium bicarbonate, sodium diacetate, sodiumpropionate, streptomycin (744), sulphur (754), TCMTB, tecloftalam,tecnazene (TCNB) (767), thiabendazole (790), thifluzamide (796),thiophanate (1435), thiophanate-methyl (802), thiram (804),tolclofos-methyl (808), tolylfluanid (810), triazoxide (821),trichoderma harzianum (825), tricyclazole (828), triforine (838),triphenyltin hydroxide (347), validamycin (846), vinclozolin (849),zineb (855), ziram (856), zoxamide (857),1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC-Name) (910),2,4-dichlorophenyl benzenesulfonate (IUPAC-/Chemical Abstracts-Name)(1059), 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC-Name) (1295),4-chlorophenyl phenyl sulfone (IUPAC-Name) (981),

a compound of formula B-5.1, a compound of formula B-5.2, a compound offormula B-5.3, a compound of formula B-5.4, a compound of formula B-5.5,a compound of formula B-5.6, a compound of formula B-5.7, compoundB-5.8, compound B-5.9, compound B-5.10, compound B-5.11, compoundB-5.12, compound B-5.13, compound B-5.14, compound B-5.15, compoundB-5.16, compound B-5.17 and compound B-5.18;

a plant-bioregulator selected from the group consisting of

acibenzolar-S-methyl (6), chlormequat chloride (137), ethephon (307),mepiquat chloride (509) and trinexapc-ethyl (841);

an insecticide selected from the group consisting of

abamectin (1), clothianidin (165), emamectin benzoate (291),imidacloprid (458), tefluthrin (769), thiamethoxam (792), and glyphosate(419), a compound of formula V

fomesafen, and (B9) a racemic compound of formula VIa (syn)

wherein Ra₇ is trifluoromethyl or difluoromethyl; a racemic mixture offormula VIb (anti)

wherein Ra₇ is trifluoromethyl or difluoromethyl; a compound of formulaVIc

which is an epimeric mixture of racemic compounds of formulae F-10 (syn)and F-11 (anti), wherein the ratio from racemic compounds of formulaF-10 (syn) to racemic compounds of formula F-11 (anti) is from 1000:1 to1:1000 and wherein Ra₇ is trifluoromethyl or difluoromethyl.

Further examples of especially suitable compounds as component (B) arecompounds selected from the following group Q:

Group Q: Especially Suitable Compounds as Component (B) in theCompositions According to the Invention:

a strobilurin fungicide selected from the group consisting ofazoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl,metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin;trifloxystrobin and a compound of formula B-1.1;

an azole fungicide selected from the group consisting of azaconazole,bromuconazole, cyproconazole, difenoconazole, diniconazole,diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole,flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole,ipconazole, metconazole, myclobutanil, oxpoconazole, pefurazoate,penconazole, prochloraz, propiconazole, prothioconazole, simeconazole,tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole,triticonazole, diclobutrazol, etaconazole, furconazole, furconazole-cisand quinconazole;

a morpholine fungicide selected from the group consisting of aldimorph,dodemorph, fenpropimorph, tridemorph, fenpropidin, spiroxamine,piperalin and a compound of formula B-3.1;

an anilino-pyrimidine fungicide selected from the group consisting ofcyprodinil, mepanipyrim and pyrimethanil;

a fungicide selected from the group consisting of benalaxyl,benalaxyl-M, benomyl, bitertanol, boscalid, captan, carboxin,carpropamid, chlorothalonil, copper, cyazofamid, cymoxanil,diethofencarb, dithianon, famoxadone, fenamidone, fenhexamide,fenoxycarb, fenpiclonil, fluazinam, fludioxonil, flutolanil, folpet,guazatine, hymexazole, iprodione, lufenuron, mancozeb, metalaxyl,mefenoxam, metrafenone, nuarimol, paclobutrazol, pencycuron,penthiopyrad, procymidone, proquinazid, pyroquilon, quinoxyfen,silthiofam, sulfur, thiabendazole, thiram, triazoxide, tricyclazole, acompound of formula B-5.1, a compound of formula B-5.2, a compound offormula B-5.3, a compound of formula B-5.4, a compound of formula B-5.5,a compound of formula B-5.6, a compound of formula B-5.7, a compound offormula B-5.8, a compound of formula B-5.9, a compound of formula B-5.10and a compound of formula B-5.12;

a plant-bioregulator selected from acibenzolar-S-methyl, chlormequatchloride, ethephon, mepiquat chloride and trinexapc-ethyl;

an insecticide selected from abamectin, emamectin benzoate, tefluthrin,thiamethoxam, and glyphosate, a compound of formula V

fomesafen, and (B9) a racemic compound of formula VIa (syn)

wherein Ra₇ is trifluoromethyl or difluoromethyl; a racemic mixture offormula VIb (anti)

wherein Ra₇ is trifluoromethyl or difluoromethyl; a compound of formulaVIc

which is an epimeric mixture of racemic compounds of formulae F-10 (syn)and F-11 (anti), wherein the ratio from racemic compounds of formulaF-10 (syn) to racemic compounds of formula F-11 (anti) is from 1000:1 to1:1000 and wherein Ra₇ is trifluoromethyl or difluoromethyl.

Throughout this document the expression “composition” stands for thevarious mixtures or combinations of components (A) and (B), for examplein a single “ready-mix” form, in a combined spray mixture composed fromseparate formulations of the single active ingredient components, suchas a “tank-mix”, and in a combined use of the single active ingredientswhen applied in a sequential manner, i.e. one after the other with areasonably short period, such as a few hours or days. The order ofapplying the components (A) and (B) is not essential for working thepresent invention.

The compositions according to the invention may also comprise more thanone of the active components (B), if, for example, a broadening of thespectrum of phytopathogenic disease control is desired. For instance, itmay be advantageous in the agricultural practice to combine two or threecomponents (B) with component (A). An example is a compositioncomprising a compound of formula (I), azoxystrobin and cyproconazole.

Further examples for compositions according to the present inventionwhich comprise three active ingredients are defined as embodiments E1and E2:

Embodiment E1:

The term “TX1” means: “the compound A-1.1+a compound selected from thegroup P”

Dimoxystrobin+TX1, fluoxastrobin+TX1, kresoxim-methyl+TX1,metominostrobin+TX1, orysastrobin+TX1, picoxystrobin+TX1,pyraclostrobin+TX1, trifloxystrobin+TX1, a compound of formulaB-1.1+TX1,

azaconazole+TX1, bromuconazole+TX1, cyproconazole+TX1,difenoconazole+TX1, diniconazole+TX1, diniconazole-M+TX1,epoxiconazole+TX1, fenbuconazole+TX1, fluquinconazole+TX1,flusilazole+TX1, flutriafol+TX1, hexaconazole+TX1, imazalil+TX1,imibenconazole+TX1, ipconazole+TX1, metconazole+TX1, myclobutanil+TX1,oxpoconazole+TX1, pefurazoate+TX1, penconazole+TX1, prochloraz+TX1,propiconazole+TX1, prothioconazole+TX1, simeconazole+TX1,tebuconazole+TX1, tetraconazole+TX1, triadimefon+TX1, triadimenol+TX1,triflumizole+TX1, triticonazole+TX1, diclobutrazol+TX1, etaconazole+TX1,furconazole+TX1, furconazole-cis+TX1, quinconazole+TX1, aldimorph+TX1,dodemorph+TX1, fenpropimorph+TX1, tridemorph+TX1, fenpropidin+TX1,spiroxamine+TX1, piperalin+TX1, a compound of formula B-3.1+TX1,cyprodinil+TX1, mepanipyrim+TX1, pyrimethanil+TX1, benalaxyl+TX1,benalaxyl-M+TX1, benomyl+TX1, bitertanol+TX1, boscalid+TX1, captan+TX1,carboxin+TX1, carpropamid+TX1, chlorothalonil+TX1, copper+TX1,cyazofamid+TX1, cymoxanil+TX1, diethofencarb+TX1, dithianon+TX1,famoxadone+TX1, fenamidone+TX1, fenhexamide+TX1, fenoxycarb+TX1,fenpiclonil+TX1, fluazinam+TX1, fludioxonil+TX1, flutolanil+TX1,folpet+TX1, guazatine+TX1, hymexazole+TX1, iprodione+TX1, lufenuron+TX1,mancozeb+TX1, metalaxyl+TX1, mefenoxam+TX1, metrafenone+TX1,nuarimol+TX1, paclobutrazol+TX1, pencycuron+TX1, penthiopyrad+TX1,procymidone+TX1, proquinazid+TX1, pyroquilon+TX1, quinoxyfen+TX1,silthiofam+TX1, sulfur+TX1, thiabendazole+TX1, thiram+TX1,triazoxide+TX1, tricyclazole+TX1, a compound of formula B-5.1+TX1, acompound of formula B-5.2+TX1, a compound of formula B-5.3+TX1, acompound of formula B-5.4+TX1, a compound of formula B-5.5+TX1, acompound of formula B-5.6+TX1, a compound of formula B-5.7+TX1, acompound of formula B-5.8+TX1, a compound of formula B-5.9+TX1, acompound of formula B-5.10+TX1, a compound of formula B-5.12+TX1,acibenzolar-S-methyl+TX1, chlormequat chloride+TX1, ethephon+TX1,mepiquat chloride+TX1, trinexapc-ethyl+TX1, abamectin+TX1, emamectinbenzoate+TX1, tefluthrin+TX1, thiamethoxam+TX1 and glyphosate+TX1.

Embodiment E2:

The term “TX2” means: “the compound A-1.2+a compound selected from thegroup P”.

Dimoxystrobin+TX2, fluoxastrobin+TX2, kresoxim-methyl+TX2,metominostrobin+TX2, orysastrobin+TX2, picoxystrobin+TX2,pyraclostrobin+TX2, trifloxystrobin+TX2, a compound of formulaB-1.1+TX2,

azaconazole+TX2, bromuconazole+TX2, cyproconazole+TX2,difenoconazole+TX2, diniconazole+TX2, diniconazole-M+TX2,epoxiconazole+TX2, fenbuconazole+TX2, fluquinconazole+TX2,flusilazole+TX2, flutriafol+TX2, hexaconazole+TX2, imazalil+TX2,imibenconazole+TX2, ipconazole+TX2, metconazole+TX2, myclobutanil+TX2,oxpoconazole+TX2, pefurazoate+TX2, penconazole+TX2, prochloraz+TX2,propiconazole+TX2, prothioconazole+TX2, simeconazole+TX2,tebuconazole+TX2, tetraconazole+TX2, triadimefon+TX2, triadimenol+TX2,triflumizole+TX2, triticonazole+TX2, diclobutrazol+TX2, etaconazole+TX2,furconazole+TX2, furconazole-cis+TX2, quinconazole+TX2, aldimorph+TX2,dodemorph+TX2, fenpropimorph+TX2, tridemorph+TX2, fenpropidin+TX2,spiroxamine+TX2, piperalin+TX2, a compound of formula B-3.1+TX2,cyprodinil+TX2, mepanipyrim+TX2, pyrimethanil+TX2, benalaxyl+TX2,benalaxyl-M+TX2, benomyl+TX2, bitertanol+TX2, boscalid+TX2, captan+TX2,carboxin+TX2, carpropamid+TX2, chlorothalonil+TX2, copper+TX2,cyazofamid+TX2, cymoxanil+TX2, diethofencarb+TX2, dithianon+TX2,famoxadone+TX2, fenamidone+TX2, fenhexamide+TX2, fenoxycarb+TX2,fenpiclonil+TX2, fluazinam+TX2, fludioxonil+TX2, flutolanil+TX2,folpet+TX2, guazatine+TX2, hymexazole+TX2, iprodione+TX2, lufenuron+TX2,mancozeb+TX2, metalaxyl+TX2, mefenoxam+TX2, metrafenone+TX2,nuarimol+TX2, paclobutrazol+TX2, pencycuron+TX2, penthiopyrad+TX2,procymidone+TX2, proquinazid+TX2, pyroquilon+TX2, quinoxyfen+TX2,silthiofam+TX2, sulfur+TX2, thiabendazole+TX2, thiram+TX2,triazoxide+TX2, tricyclazole+TX2, a compound of formula B-5.1+TX2, acompound of formula B-5.2+TX2, a compound of formula B-5.3+TX2, acompound of formula B-5.4+TX2, a compound of formula B-5.5+TX2, acompound of formula B-5.6+TX2, a compound of formula B-5.7+TX2, acompound of formula B-5.8+TX2, a compound of formula B-5.9+TX2, acompound of formula B-5.10+TX2, a compound of formula B-5.12+TX2,acibenzolar-S-methyl+TX2, chlormequat chloride+TX2, ethephon+TX2,mepiquat chloride+TX2, trinexapc-ethyl+TX2, abamectin+TX2, emamectinbenzoate+TX2, tefluthrin+TX2, thiamethoxam+TX2 and glyphosate+TX2.

The embodiments E1 and E2 define compositions according to the presentinvention which comprise 3 active ingredients. In said embodiments, themixing partner selected from the group P has to be different from theother described mixing partners. For example, the composition“cyproconazole+TX1” means compositions comprising as active ingredientscyproconazole, the compound A-1.1+a compound selected from the group P.In said compositions, the compound selected from the group P isdifferent from cyproconazole.

The following compositions are preferred:

A composition comprising (A) compound A-1.1 and (B) a compound selectedfrom the group P. An example of such a composition is a compositioncomprising the compound A-1.1 and the first compound from the group P,which is azoxystrobin.

A composition comprising (A) compound A-1.1 and (B) a compound selectedfrom the group Q. An example of such a composition is a compositioncomprising the compound A-1.1 and the second compound from the group Q,which is dimoxystrobin.

A composition comprising (A) compound A-1.1 and (B) a strobilurinfungicide.

A composition comprising (A) compound A-1.1 and (B) an azole fungicide.

A composition comprising (A) compound A-1.1 and (B) a morpholinefungicide.

A composition comprising (A) compound A-1.1 and (B) an anilinopyrimidinefungicide.

A composition comprising (A) compound A-1.1 and the insecticide offormula B-7.1.

A composition comprising (A) compound A-1.1 and (B) a glyphosate.

A composition comprising (A) compound A-1.1 and a fungicide selectedfrom azoxystrobin, fluoxastrobin, picoxystrobin, pyraclostrobin,trifloxystrobin, cyproconazole, difenoconazole, epoxiconazole,flutriafol, ipconazole, metconazole, myclobutanil, penconazole,propiconazole, prothioconazole, tebuconazole, tetraconazole,fenpropidin, cyprodinil, chlorothalonil, dithianon, fluazinam,fludioxonil, metrafenone, compound B-5.1 and compound B-5.4.

A composition comprising (A) compound A-1.1 and a fungicide selectedfrom azoxystrobin, fluoxastrobin, picoxystrobin, pyraclostrobin,trifloxystrobin, cyproconazole, epoxiconazole, flutriafol, ipconazole,metconazole, myclobutanil, propiconazole, prothioconazole, tebuconazole,tetraconazole and chlorothalonil.

A composition comprising (A) compound A-1.2 and (B) a compound selectedfrom the group P.

A composition comprising (A) compound A-1.2 and (B) a compound selectedfrom the group Q.

A composition comprising (A) compound A-1.2 and (B) a strobilurinfungicide.

A composition comprising (A) compound A-1.2 and (B) an azole fungicide.

A composition comprising (A) compound A-1.2 and (B) a morpholinefungicide.

A composition comprising (A) compound A-1.2 and (B) an anilinopyrimidinefungicide.

A composition comprising (A) compound A-1.2 and the insecticide offormula B-7.1.

A composition comprising (A) compound A-1.2 and (B) a glyphosate.

A composition comprising (A) compound A-1.2 and a fungicide selectedfrom azoxystrobin, fluoxastrobin, picoxystrobin, pyraclostrobin,trifloxystrobin, cyproconazole, difenoconazole, epoxiconazole,flutriafol, ipconazole, metconazole, myclobutanil, penconazole,propiconazole, prothioconazole, tebuconazole, tetraconazole,fenpropidin, cyprodinil, chlorothalonil, dithianon, fluazinam,fludioxonil, metrafenone, compound B-5.1 and compound B-5.4.

A composition comprising (A) compound A-1.2 and a fungicide selectedfrom azoxystrobin, fluoxastrobin, picoxystrobin, pyraclostrobin,trifloxystrobin, cyproconazole, epoxiconazole, flutriafol, ipconazole,metconazole, myclobutanil, propiconazole, prothioconazole, tebuconazole,tetraconazole and chlorothalonil.

A composition comprising (A) compound A-1.3 and (B) a compound selectedfrom the group P.

A composition comprising (A) compound A-1.3 and (B) a compound selectedfrom the group Q.

A composition comprising (A) compound A-1.3 and (B) a strobilurinfungicide.

A composition comprising (A) compound A-1.3 and (B) an azole fungicide.

A composition comprising (A) compound A-1.3 and (B) a morpholinefungicide.

A composition comprising (A) compound A-1.3 and (B) an anilinopyrimidinefungicide.

A composition comprising (A) compound A-1.3 and the insecticide offormula B-7.1.

A composition comprising (A) compound A-1.3 and (B) a glyphosate.

A composition comprising (A) compound A-1.3 and a fungicide selectedfrom azoxystrobin, fluoxastrobin, picoxystrobin, pyraclostrobin,trifloxystrobin, cyproconazole, difenoconazole, epoxiconazole,flutriafol, ipconazole, metconazole, myclobutanil, penconazole,propiconazole, prothioconazole, tebuconazole, tetraconazole,fenpropidin, cyprodinil, chlorothalonil, dithianon, fluazinam,fludioxonil, metrafenone, compound B-5.1 and compound B-5.4.

A composition comprising (A) compound A-1.3 and a fungicide selectedfrom azoxystrobin, fluoxastrobin, picoxystrobin, pyraclostrobin,trifloxystrobin, cyproconazole, epoxiconazole, flutriafol, ipconazole,metconazole, myclobutanil, propiconazole, prothioconazole, tebuconazole,tetraconazole and chlorothalonil.

A composition comprising (A) compound A-1.4 and (B) a compound selectedfrom the group P.

A composition comprising (A) compound A-1.5 and (B) a compound selectedfrom the group P.

A composition comprising (A) compound A-1.6 and (B) a compound selectedfrom the group P.

The compositions according to the invention are effective againstharmful microorganisms, such as microorganisms, that causephytopathogenic diseases, in particular against phytopathogenic fungiand bacteria.

The compositions according to the invention are effective especiallyagainst phytopathogenic fungi belonging to the following classes:Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia,Mycosphaerella, Uncinula); Basidiomycetes (e.g. the genus Hemileia,Rhizoctonia, Phakopsora, Puccinia, Ustilago, Tilletia); Fungi imperfecti(also known as Deuteromycetes; e.g. Botrytis, Helminthosporium,Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyriculariaand Pseudocercosporella); Oomycetes (e.g. Phytophthora, Peronospora,Pseudoperonospora, Albugo, Bremia, Pythium, Pseudosclerospora,Plasmopara).

According to the invention “useful plants” typically comprise thefollowing species of plants: grape vines; cereals, such as wheat,barley, rye or oats; beet, such as sugar beet or fodder beet; fruits,such as pomes, stone fruits or soft fruits, for example apples, pears,plums, peaches, almonds, cherries, strawberries, raspberries orblackberries; leguminous plants, such as beans, lentils, peas orsoybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers,coconut, castor oil plants, cocoa beans or groundnuts; cucumber plants,such as marrows, cucumbers or melons; fibre plants, such as cotton,flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit ormandarins; vegetables, such as spinach, lettuce, asparagus, cabbages,carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceae,such as avocados, cinnamon or camphor; maize; tobacco; nuts; coffee;sugar cane; tea; vines; hops; durian; bananas; natural rubber plants;turf or ornamentals, such as flowers, shrubs, broad-leaved trees orevergreens, for example conifers. This list does not represent anylimitation.

The term “useful plants” is to be understood as including also usefulplants that have been rendered tolerant to herbicides like bromoxynil orclasses of herbicides (such as, for example, HPPD inhibitors, ALSinhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron,EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS(glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase)inhibitors) as a result of conventional methods of breeding or geneticengineering. An example of a crop that has been rendered tolerant toimidazolinones, e.g. imazamox, by conventional methods of breeding(mutagenesis) is Clearfield® summer rape (Canola). Examples of cropsthat have been rendered tolerant to herbicides or classes of herbicidesby genetic engineering methods include glyphosate- andglufosinate-resistant maize varieties commercially available under thetrade names RoundupReady, Herculex I® and LibertyLink®.

The term “useful plants” is to be understood as including also usefulplants which have been so transformed by the use of recombinant DNAtechniques that they are capable of synthesising one or more selectivelyacting toxins, such as are known, for example, from toxin-producingbacteria, especially those of the genus Bacillus.

The term “useful plants” is to be understood as including also usefulplants which have been so transformed by the use of recombinant DNAtechniques that they are capable of synthesising antipathogenicsubstances having a selective action, such as, for example, theso-called “pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392225). Examples of such antipathogenic substances and transgenic plantscapable of synthesising such antipathogenic substances are known, forexample, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191. Themethods of producing such transgenic plants are generally known to theperson skilled in the art and are described, for example, in thepublications mentioned above.

The term “locus” of a useful plant as used herein is intended to embracethe place on which the useful plants are growing, where the plantpropagation materials of the useful plants are sown or where the plantpropagation materials of the useful plants will be placed into the soil.An example for such a locus is a field, on which crop plants aregrowing.

The term “plant propagation material” is understood to denote generativeparts of the plant, such as seeds, which can be used for themultiplication of the latter, and vegetative material, such as cuttingsor tubers, for example potatoes. There may be mentioned for exampleseeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes andparts of plants. Germinated plants and young plants which are to betransplanted after germination or after emergence from the soil, mayalso be mentioned. These young plants may be protected beforetransplantation by a total or partial treatment by immersion. Preferably“plant propagation material” is understood to denote seeds.

The compositions of the present invention may also be used in the fieldof protecting storage goods against attack of fungi. According to thepresent invention, the term “storage goods” is understood to denotenatural substances of vegetable and/or animal origin and their processedforms, which have been taken from the natural life cycle and for whichlong-term protection is desired. Storage goods of vegetable origin, suchas plants or parts thereof, for example stalks, leafs, tubers, seeds,fruits or grains, can be protected in the freshly harvested state or inprocessed form, such as pre-dried, moistened, comminuted, ground,pressed or roasted. Also falling under the definition of storage goodsis timber, whether in the form of crude timber, such as constructiontimber, electricity pylons and barriers, or in the form of finishedarticles, such as furniture or objects made from wood. Storage goods ofanimal origin are hides, leather, furs, hairs and the like. Thecompositions according the present invention can prevent disadvantageouseffects such as decay, discoloration or mold. Preferably “storage goods”is understood to denote natural substances of vegetable origin and/ortheir processed forms, more preferably fruits and their processed forms,such as pomes, stone fruits, soft fruits and citrus fruits and theirprocessed forms. In another preferred embodiment of the invention“storage goods” is understood to denote wood.

Therefore a further aspect of the present invention is a method ofprotecting storage goods, which comprises applying to the storage goodsa composition according to the invention.

The compositions of the present invention may also be used in the fieldof protecting technical material against attack of fungi. According tothe present invention, the term “technical material” includes paper;carpets; constructions; cooling and heating systems; wall-boards;ventilation and air conditioning systems and the like; preferably“technical material” is understood to denote wall-boards. Thecompositions according the present invention can prevent disadvantageouseffects such as decay, discoloration or mold.

The compositions according to the invention are particularly effectiveagainst powdery mildews; rusts; leafspot species; early blights andmolds; especially against Septoria, Puccinia, Erysiphe, Pyrenophora andTapesia in cereals; Phakopsora in soybeans; Hemileia in coffee;Phragmidium in roses; Alternaria in potatoes, tomatoes and cucurbits;Sclerotinia in turf, vegetables, sunflower and oil seed rape; black rot,red fire, powdery mildew, grey mold and dead arm disease in vine;Botrytis cinerea in fruits; Monilinia spp. in fruits and Penicilliumspp. in fruits.

The compositions according to the invention are furthermore particularlyeffective against seedborne and soilborne diseases, such as Alternariaspp., Ascochyta spp., Botrytis cinerea, Cercospora spp., Clavicepspurpurea, Cochliobolus sativus, Colletotrichum spp., Epicoccum spp.,Fusarium graminearum, Fusarium moniliforme, Fusarium oxysporum, Fusariumproliferatum, Fusarium solani, Fusarium subglutinans, Gaumannomycesgraminis, Helminthosporium spp., Microdochium nivale, Phoma spp.,Pyrenophora graminea, Pyricularia oryzae, Rhizoctonia solani,Rhizoctonia cerealis, Sclerotinia spp., Septoria spp., Sphacelothecareilliana, Tilletia spp., Typhula incarnata, Urocystis occulta, Ustilagospp. or Verticillium spp.; in particular against pathogens of cereals,such as wheat, barley, rye or oats; maize; rice; cotton; soybean; turf;sugarbeet; oil seed rape; potatoes; pulse crops, such as peas, lentilsor chickpea; and sunflower.

The compositions according to the invention are furthermore particularlyeffective against post harvest diseases such as Botrytis cinerea,Colletotrichum musae, Curvularia lunata, Fusarium semitecum, Geotrichumcandidum, Monilinia fructicola, Monilinia fructigena, Monilinia laxa,Mucor piriformis, Penicilium italicum, Penicilium solitum, Penicilliumdigitatum or Penicillium expansum in particular against pathogens offruits, such as pomefruits, for example apples and pears, stone fruits,for example peaches and plums, citrus, melons, papaya, kiwi, mango,berries, for example strawberries, avocados, pomegranates and bananas,and nuts.

The compositions according to the invention are particularly useful forcontrolling the following diseases on the following crops:

Alternaria species in fruit and vegetables; Ascochyta species in pulsecrops; Botrytis cinerea in strawberries, tomatoes, sunflower, pulsecrops, vegetables and grapes, such as Botrytis cinerea on grape;Cercospora arachidicola in peanuts; Cochliobolus sativus in cereals;Colletotrichum species in pulse crops; Erysiphe species in cereals; suchas Erysiphe graminis on wheat and Erysiphe graminis on barley; Erysiphecichoracearum and Sphaerotheca fuliginea in cucurbits; Fusarium speciesin cereals and maize; Gäumannomyces graminis in cereals and lawns;Helminthosporium species in maize, rice and potatoes; Hemileia vastatrixon coffee; Microdochium species in wheat and rye; Mycosphaerellafijiensis in banana; Phakopsora species in soybeans, such as Phakopsorapachyrizi in soybeans; Puccinia species in cereals, broadleaf crops andperennial plants; such as Puccinia recondita on wheat, Pucciniastriiformis on wheat and Puccinia recondita on barley;Pseudocercosporella species in cereals, such as Pseudocercosporellaherpotrichoides in wheat; Phragmidium mucronatum in roses; Podosphaeraspecies in fruits; Pyrenophora species in barley, such as Pyrenophorateres on barley; Pyricularia oryzae in rice; Ramularia collo-cygni inbarley; Rhizoctonia species in cotton, soybean, cereals, maize,potatoes, rice and lawns, such as Rhizoctonia solani on potato, rice,turf and cotton; Rhynchosporium secalis on barley, Rhynchosporiumsecalis on rye; Sclerotinia species in lawns, lettuce, vegetables andoil seed rape, such as Sclerotinia sclerotiorum on oilseed rape andSclerotinia homeocarpa on turf; Septoria species in cereals, soybean andvegetables, such as Septoria tritici on wheat, Septoria nodorum on wheatand Septoria glycines on soybean; Sphacelotheca reilliana in maize;Tilletia species in cereals; Uncinula necator, Guignardia bidwellii andPhomopsis viticola in vines; Urocystis occulta in rye; Uromyces speciesin beans; Ustilago species in cereals and maize; Venturia species infruits, such as Venturia inequalis on apple; Monilinia species onfruits; Penicillium species on citrus and apples.

In general, the weight ratio of component (A) to component (B) is from2000:1 to 1:1000. A non-limiting example for such weight ratios iscompound of formula I:compound of formula B-2 is 10:1. The weight ratioof component (A) to component (B) is preferably from 100:1 to 1:100;more preferably from 20:1 to 1:50.

It has been found, surprisingly, that certain weight ratios of component(A) to component (B) are able to give rise to synergistic activity.Therefore, a further aspect of the invention are compositions, whereincomponent (A) and component (B) are present in the composition inamounts producing a synergistic effect. This synergistic activity isapparent from the fact that the fungicidal activity of the compositioncomprising component (A) and component (B) is greater than the sum ofthe fungicidal activities of component (A) and of component (B). Thissynergistic activity extends the range of action of component (A) andcomponent (B) in two ways. Firstly, the rates of application ofcomponent (A) and component (B) are lowered whilst the action remainsequally good, meaning that the active ingredient mixture still achievesa high degree of phytopathogen control even where the two individualcomponents have become totally ineffective in such a low applicationrate range. Secondly, there is a substantial broadening of the spectrumof phytopathogens that can be controlled.

A synergistic effect exists whenever the action of an active ingredientcombination is greater than the sum of the actions of the individualcomponents. The action to be expected E for a given active ingredientcombination obeys the so-called COLBY formula and can be calculated asfollows (COLBY, S. R. “Calculating synergistic and antagonisticresponses of herbicide combination”. Weeds, Vol. 15, pages 20-22; 1967):

ppm=milligrams of active ingredient (=a.i.) per liter of spray mixture

X=% action by active ingredient A) using p ppm of active ingredient

Y=% action by active ingredient B) using q ppm of active ingredient.

According to COLBY, the expected (additive) action of active ingredientA+B) using p+q ppm of active ingredient is

$E = {X + Y - \frac{X \cdot Y}{100}}$

If the action actually observed (O) is greater than the expected action(E), then the action of the combination is super-additive, i.e. there isa synergistic effect. In mathematical terms, synergism corresponds to apositive value for the difference of (O-E). In the case of purelycomplementary addition of activities (expected activity), saiddifference (O-E) is zero. A negative value of said difference (O-E)signals a loss of activity compared to the expected activity.

However, besides the actual synergistic action with respect tofungicidal activity, the compositions according to the invention canalso have further surprising advantageous properties. Examples of suchadvantageous properties that may be mentioned are: more advantageousdegradability; improved toxicological and/or ecotoxicological behaviour;or improved characteristics of the useful plants including: emergence,crop yields, more developed root system, tillering increase, increase inplant height, bigger leaf blade, less dead basal leaves, strongertillers, greener leaf colour, less fertilizers needed, less seedsneeded, more productive tillers, earlier flowering, early grainmaturity, less plant verse (lodging), increased shoot growth, improvedplant vigor, and early germination.

Some compositions according to the invention have a systemic action andcan be used as foliar, soil and seed treatment fungicides.

With the compositions according to the invention it is possible toinhibit or destroy the phytopathogenic microorganisms which occur inplants or in parts of plants (fruit, blossoms, leaves, stems, tubers,roots) in different useful plants, while at the same time the parts ofplants which grow later are also protected from attack byphytopathogenic microorganisms.

The compositions according to the invention can be applied to thephytopathogenic microorganisms, the useful plants, the locus thereof,the propagation material thereof, storage goods or technical materialsthreatened by microorganism attack.

The compositions according to the invention may be applied before orafter infection of the useful plants, the propagation material thereof,storage goods or technical materials by the microorganisms.

The amount of a composition according to the invention to be applied,will depend on various factors, such as the compounds employed; thesubject of the treatment, such as, for example plants, soil or seeds;the type of treatment, such as, for example spraying, dusting or seeddressing; the purpose of the treatment, such as, for exampleprophylactic or therapeutic; the type of fungi to be controlled or theapplication time.

When applied to the useful plants component (A) is typically applied ata rate of 5 to 2000 g a.i./ha, particularly 10 to 1000 g a.i./ha, e.g.50, 75, 100 or 200 g a.i./ha, typically in association with 1 to 5000 ga.i./ha, particularly 2 to 2000 g a.i./ha, e.g. 100, 250, 500, 800,1000, 1500 g a.i./ha of component (B).

In agricultural practice the application rates of the compositionsaccording to the invention depend on the type of effect desired, andtypically range from 20 to 4000 g of total composition per hectare.

When the compositions according to the invention are used for treatingseed, rates of 0.001 to 50 g of a compound of component (A) per kg ofseed, preferably from 0.01 to 10 g per kg of seed, and 0.001 to 50 g ofa compound of component (B), per kg of seed, preferably from 0.01 to 10g per kg of seed, are generally sufficient.

The composition of the invention may be employed in any conventionalform, for example in the form of a twin pack, a powder for dry seedtreatment (DS), an emulsion for seed treatment (ES), a flowableconcentrate for seed treatment (FS), a solution for seed treatment (LS),a water dispersible powder for seed treatment (WS), a capsule suspensionfor seed treatment (CF), a gel for seed treatment (GF), an emulsionconcentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE),a capsule suspension (CS), a water dispersible granule (WG), anemulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion,oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oilmiscible flowable (OF), an oil miscible liquid (OL), a solubleconcentrate (SL), an ultra-low volume suspension (SU), an ultra-lowvolume liquid (UL), a technical concentrate (TK), a dispersibleconcentrate (DC), a wettable powder (WP) or any technically feasibleformulation in combination with agriculturally acceptable adjuvants.

Such compositions may be produced in conventional manner, e.g. by mixingthe active ingredients with at least one appropriate inert formulationadjuvant (for example, diluents, solvents, fillers and optionally otherformulating ingredients such as surfactants, biocides, anti-freeze,stickers, thickeners and compounds that provide adjuvancy effects). Alsoconventional slow release formulations may be employed where longlasting efficacy is intended. Particularly formulations to be applied inspraying forms, such as water dispersible concentrates (e.g. EC, SC, DC,OD, SE, EW, EO and the like), wettable powders and granules, may containsurfactants such as wetting and dispersing agents and other compoundsthat provide adjuvancy effects, e.g. the condensation product offormaldehyde with naphthalene sulphonate, an alkylarylsulphonate, alignin sulphonate, a fatty alkyl sulphate, and ethoxylated alkylphenoland an ethoxylated fatty alcohol.

The compositions according to the invention may also comprise furtherpesticides, such as, for example, fungicides, insecticides orherbicides.

A seed dressing formulation is applied in a manner known per se to theseeds employing the compositions according to the invention and adiluent in suitable seed dressing formulation form, e.g. as an aqueoussuspension or in a dry powder form having good adherence to the seeds.Such seed dressing formulations are known in the art. Seed dressingformulations may contain the single active ingredients or thecombination of active ingredients in encapsulated form, e.g. as slowrelease capsules or microcapsules.

In general, the formulations include from 0.01 to 90% by weight ofactive agent, from 0 to 20% agriculturally acceptable surfactant and 10to 99.99% solid or liquid formulation inerts and adjuvant(s), the activeagent consisting of at least a compound of component (A) together with acompound of component (B), and optionally other active agents,particularly microbiocides or conservatives or the like. Concentratedforms of compositions generally contain in between about 2 and 80%,preferably between about 5 and 70% by weight of active agent.Application forms of formulation may for example contain from 0.01 to20% by weight, preferably from 0.01 to 5% by weight of active agent.Whereas commercial products will preferably be formulated asconcentrates, the end user will normally employ diluted formulations.

Surprisingly it has been found that compounds of formula (I)

wherein R₁ is difluoromethyl or trifluoromethyl and X is chloro, fluoroor bromo; have good activity against soybean rust diseases, such asdiseases caused by Phakopsora pachyrhizi and/or Phakopsora meibomiae.

Accordingly a further aspect of the present invention is a method ofcontrolling rust diseases on soybean plants, which comprises applying tothe soybean plants, the locus thereof or propagation material thereof acomposition comprising a compound of formula (I).

Preferred is a method, which comprises applying to the soybean plants orto the locus thereof a composition comprising a compound of formula (I),preferably to the soybean plants.

Further preferred is a method, which comprises applying to thepropagation material of the soybean plants a composition comprising acompound of formula (I).

The methods according to the invention, especially when a compound offormula (I) is used in combination with at least one compound (B) asdescribed above, also allows good control of other harmful fungifrequently encountered in soybean plants. The most important fungaldiseases in soybeans being Phakopsora pachyrhizi, Microsphaera diffusa,Cercospora kikuchi, Cercospora sojina, Septoria glycines andColletotrichum truncatum, some of which comprise the so-called “lateseason disease complex”, and furthermore Rhizoctonia solani, Corynesporacassiicola, Sclerotinia sclerotiorum and Sclerosium rolfsii.

Further characteristics of compositions comprising compounds of formula(I), their application methods to soybeans and their use rates are asdescribed for compositions comprising compounds of formula (I) andadditionally at least one component (B) as described above. Theirapplication can be both before and after the infection of the soybeanplants or parts thereof with the fungi. The treatment is preferablycarried out prior to the infection. When a compound of formula (I) isused on its own, the application rates in the method according to theinvention are as described above, e.g. typical are rates of 5 to 2000 ga.i./ha, particularly 10 to 1000 g a.i./ha, e.g. 50, 75, 100 or 200 ga.i./ha. Compounds of formula (I) can be applied to the soybean plantsonce or more than once during a growing season. For use in the methodaccording to the invention, the compounds of formula (I) can beconverted into the customary formulations described above, e.g.solutions, emulsions, suspensions, dusts, powders, pastes and granules.The use form will depend on the particular intended purpose; in eachcase, it should ensure a fine and even distribution of the compound offormula (I).

As described above for the term “useful plant”, the term “soybean plant”includes all soybean plants and all varieties, including transgenicplants. The term “soybean plant” includes especially glyphosate tolerantsoybean plants.

By “glyphosate tolerant” is meant that the plants for use in the methodsare resistant to glyphosate application or tolerant of glyphosate.Glyphosate tolerant plants are made tolerant to glyphosate byconventional breeding or having a transgenic event that providesglyphosate resistance. Some examples of such preferred transgenic plantshaving transgenic events that confer glyphosate resistance are describedin U.S. Pat. Nos. 5,914,451; 5,866,775; 5,804,425; 5,776,760; 5,633,435;5,627,061; 5,463,175; 5,312,910; 5,310,667; 5,188,642; 5,145,783;4,971,908 and 4,940,835. The use of “stacked” transgenic events in theplant is also contemplated.

Stacked transgenic events including additional herbicide-resistanttraits such as resistance to HPPD-inhibitors, sulfonyl-ureas,glufosinate and bromoxynil are widely used and described in readilyavailable resources. The stacked transgenic events may also be directedto other pesticide resistant traits, such as insecticide, nematicide,fungicide, etc resistance, which may be made by conventional breeding orintroducing a transgenic event.

Lines of transgenic glyphosate tolerant crop plants contemplated for usein the methods of the present invention include, for example, RoundupReady Soybean 40-3-2.

A “transgenic plant” refers to a plant that contains genetic materialnot found (i.e. “exogenous”) in a wild-type plant of the same species,variety or cultivar. The genetic material may include a transgene, aninsertional mutagenesis event (such as by transposon or T-DNAinsertional mutagenesis), an activation tagging sequence, a mutatedsequence, a homologous recombination event or a sequence modified bychimeraplasty. Typically, the foreign genetic material has beenintroduced into the plant by human manipulation, but any method can beused as one of skill in the art recognizes. A transgenic plant maycontain an expression vector or cassette. The expression cassettetypically comprises a polypeptide-encoding sequence operably linked(i.e., under regulatory control of) to appropriate inducible orconstitutive regulatory sequences that allow for the expression of thepolypeptide. The expression cassette can be introduced into a plant bytransformation or by breeding after transformation of a parent plant. Aspreviously described a plant refers to a whole plant, includingseedlings and mature plants, as well as to a plant part, such as seed,fruit, leaf, or root, plant tissue, plant cells or any other plantmaterial, e.g., a plant explant, as well as to progeny thereof, and toin vitro systems that mimic biochemical or cellular components orprocesses in a cell.

If the soybean plants are glyphosate tolerant, then it is especiallypreferred that combinations of compounds of formula (I) and glyphosateare used. Above is given a general guidance to typical glyphosateapplication rates—as glyphosate is one of the compounds (B)—but theoptimal rate to be used depends on many factors including theenvironment and should be determined under actual use conditions.Preferably, a rate of application of a glyphosate compound from about400 g acid equivalent (ae)/ha to about 3400 g ae/ha of glyphosate iseffective in controlling, preventing or treating a soybean rustpathogen, such as Asian soybean rust, in accordance with the method ofthe present invention. Yet more preferable are rates of applicationrange from about 800 g ae/ha to 1700 g ae/ha. Generally,glyphosate-containing compositions can be applied, if applied only once,at a rate of 960 g ae/ha; if applied twice the rate can vary from 1200to 1680 g ae/ha. When more than one application of glyphosate-containingcompositions to the soybean plants are performed, it is not neccessarythat all glyphosate-containing compositions contain also a compound offormula (I). The rates and number of glyphosate-applications may varyaccording to the particular conditions. Preferably,glyphosate-containing compositions are applied three times with anapplication rate of 960, 720 and 400 g ae/ha respectively. In saidembodiment of the invention, the present invention also provides amethod for controlling undesired vegetation, such as harmful weeds, andcontrolling, preventing or treating soybean rust diseases in a field ofglyphosate tolerant soybean plants. Preferably, the application orapplications are timed for effective weed control and effective soybeanrust control, prevention or treatment in the treated soybean plant. Forexample, without limitation, a glyphosate-containing composition isapplied at a time when the application controls the weeds within thefield; a second glyphosate-containing composition is applied at a timewhen the glyphospate tolerant soybean plants are either at risk ofinfection or have already been infected by a soybean rust disease, saidsecond glyphosate-containing composition additionally comprises at leasta compound of formula (I). Another application of the secondglyphosate-containing composition can also be envisaged to furtherprevent infection.

The Examples which follow serve to illustrate the invention, “activeingredient” denotes a mixture of component (A) and component (B) in aspecific mixing ratio. The same formulations can be used forcompositions comprising only a compound of formula (I) as the activeingredient.

FORMULATION EXAMPLES

Wettable powders a) b) active ingredient [A):B) = 1:3(a), 1:1(b)] 25% 75% sodium lignosulfonate 5% — sodium lauryl sulfate 3%  5% sodiumdiisobutylnaphthalenesulfonate — 10% (7-8 mol of ethylene oxide) highlydispersed silicic acid 5% 10% kaolin 62%  —

The active ingredient is thoroughly mixed with the other formulationcomponents and the mixture is thoroughly ground in a suitable mill,affording wettable powders that can be diluted with water to givesuspensions of the desired concentration.

Powders for dry seed treatment a) b) active ingredient [A):B) = 1:3(a),1:1(b)] 25% 75% light mineral oil  5%  5% highly dispersed silicic acid 5% — kaolin 65% — talc — 20

The active ingredient is thoroughly mixed with the other formulationcomponents and the mixture is thoroughly ground in a suitable mill,affording powders that can be used directly for seed treatment.

Emulsifiable concentrate active ingredient (A):B) = 1:6) 10% octylphenolpolyethylene glycol ether  3% (4-5 mol of ethylene oxide) calciumdodecylbenzenesulfonate  3% castor oil polyglycol ether (35 mol ofethylene oxide)  4% cyclohexanone 30% xylene mixture 50%

Emulsions of any required dilution, which can be used in plantprotection, can be obtained from this concentrate by dilution withwater.

Dustable oowders a) b) active ingredient [A):B) = 1:6(a), 1:10(b)]  5% 6% talcum 95% — kaolin — 94%

Ready-for-use dusts are obtained by mixing the active ingredient withthe carriers and grinding the mixture in a suitable mill. Such powderscan also be used for dry dressings for seed.

Extruded granules % w/w active ingredient (A):B) = 2:1) 15% sodiumlignosulfonate  2% sodium alkyl naphthalene sulfonate  1% kaolin 82%

The active ingredient is mixed and ground with the other formulationcomponents, and the mixture is moistened with water. The mixture isextruded and then dried in a stream of air.

Suspension concentrate active ingredient (A):B) = 1:8) 40% propyleneglycol 10% nonylphenol polyethylene glycol ether (15 mol of ethyleneoxide)  6% sodium lignosulfonate 10% carboxymethylcellulose  1% siliconeoil (in the form of a 75% emulsion in water)  1% water 32%

The finely ground active ingredient is intimately mixed with the otherformulation components, giving a suspension concentrate which can bediluted in water at any desired rate. Using such dilutions, livingplants as well as plant propagation material can be treated andprotected against infestation by microorganisms, by spraying, pouring orimmersion.

Flowable concentrate for seed treatment active ingredient (A):B) = 1:8)40%  propylene glycol 5% copolymer butanol PO/EO 2% tristyrenephenoleethoxylate (with 10-20 moles EO) 2% 1,2-benzisothiazolin-3-one 0.5% monoazo-pigment calcium salt 5% silicone oil (in the form of a 75%emulsion in water) 0.2%  water 45.3%  

The finely ground active ingredient is intimately mixed with the otherformulation components, giving a suspension concentrate which can bediluted further in water to be applied to seeds. Using such dilutions,propagation material can be treated and protected against infestation bymicroorganisms, by spraying, pouring or immersion.

BIOLOGICAL EXAMPLES Example B-1 Action Against Asian Soybean Rust(Phakopsora pachyrhizi)—Leaf Disc Test

Whole soybean plants (variety brand Williams82) are treated with therecited active ingredients 4 weeks after planting. 1 day after sprayingleaf disks are cut from the first trifoliate leaf. Five repetitions ateach rate are conducted. The leaf disks are inoculated with Phakopsorapachyrhizi (Asian soybean rust) one day after treatment. Evaluation ofthe leaf disks is conducted fourteen days after inoculation and the meanpercent infestation of the five repetitions is calculated. StandardEC100 formulations are used. The rates of the active ingredients usedare given in Table B1 as g active ingredient (a.i.)/ha.

TABLE B1 Action against Asian soybean rust % Control of Phakopsorapachyrhizi g.ai./ha Cpd A-1.1 Cpd A-1.2 Cpd A-1.3 250 87 94 93 125 82 4454 62.5 36 54 36 31.25 36 39 36

Example B2 Fungicidal Action Against Botrytis cinerea (Gray Mould)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds into a microtiter plate (96-well format)the nutrient broth containing the fungal spores is added. The testplates are incubated at 24° C. and the inhibition of growth is evaluatedafter 4 days.

The expected fungicidal action is calculated according to the Colbymethod. The results are given in Tables B2:

TABLE B2 Fungicidal action against Botrytis cinerea B2.1: Compound A-1.1Azoxystrobin expected action ppm ppm % activity (Colby) 1.0000 90 0.500050 0.2500 20 0.1250 20 2.0000 0 1.0000 0 0.5000 0 0.2500 0 0.1250 01.0000 2.0000 100 90 1.0000 1.0000 100 90 1.0000 0.5000 100 90 0.50002.0000 100 50 0.5000 1.0000 100 50 0.5000 0.5000 100 50 0.5000 0.2500 9050 0.5000 0.1250 70 50 0.2500 1.0000 100 20 0.2500 0.5000 100 20 0.25000.2500 70 20 0.2500 0.1250 50 20 0.1250 0.5000 90 20 0.1250 0.2500 50 20B2.2: Compound A-1.1 Picoxystrobin expected action ppm ppm % activity(Colby) 0.5000 70 0.2500 50 0.1250 20 0.0625 20 2.0000 0 1.0000 0 0.50000 0.2500 0 0.1250 0 0.0625 0 0.5000 2.0000 100 70 0.5000 1.0000 100 700.5000 0.5000 100 70 0.5000 0.2500 100 70 0.5000 0.1250 100 70 0.25001.0000 100 50 0.2500 0.5000 100 50 0.2500 0.2500 100 50 0.2500 0.1250100 50 0.2500 0.0625 90 50 0.1250 0.5000 100 20 0.1250 0.2500 100 200.1250 0.1250 100 20 0.1250 0.0625 70 20 0.0625 0.2500 100 20 0.06250.1250 90 20 0.0625 0.0625 50 20 B2.3: Compound A-1.1 Fludioxonilexpected action ppm ppm % activity (Colby) 0.2500 50 0.1250 20 0.0625 200.0313 0 0.0156 0 0.1250 90 0.0625 20 0.0313 0 0.2500 0.0625 100 600.1250 0.0625 100 36 0.1250 0.0313 50 20 0.0625 0.0625 90 36 0.06250.0313 50 20 0.0313 0.1250 100 90 0.0313 0.0625 90 20 0.0156 0.0625 7020 B2.4: Compound A-1.2 Azoxystrobin expected action ppm ppm % activity(Colby) 2.0000 70 1.0000 50 0.5000 20 0.2500 20 2.0000 0 1.0000 0 0.50000 0.2500 0 2.0000 2.0000 100 70 2.0000 1.0000 100 70 2.0000 0.5000 10070 1.0000 2.0000 100 50 1.0000 1.0000 100 50 1.0000 0.5000 100 50 1.00000.2500 70 50 0.5000 2.0000 100 20 0.5000 1.0000 100 20 0.5000 0.5000 10020 0.5000 0.2500 50 20 0.2500 1.0000 90 20 0.2500 0.5000 70 20 0.25000.2500 50 20 B2.5: Compound A-1.2 Picoxystrobin expected action ppm ppm% activity (Colby) 2.0000 70 1.0000 50 0.5000 20 0.2500 20 0.1250 202.0000 0 1.0000 0 0.5000 0 0.2500 0 0.1250 0 2.0000 2.0000 100 70 2.00001.0000 100 70 2.0000 0.5000 100 70 1.0000 2.0000 100 50 1.0000 1.0000100 50 1.0000 0.5000 100 50 1.0000 0.2500 100 50 0.5000 2.0000 100 200.5000 1.0000 100 20 0.5000 0.5000 100 20 0.5000 0.2500 100 20 0.50000.1250 90 20 0.2500 1.0000 100 20 0.2500 0.5000 100 20 0.2500 0.2500 9020 0.2500 0.1250 70 20 0.1250 0.5000 90 20 0.1250 0.2500 70 20 0.12500.1250 50 20 B2.6: Compound A-1.2 Fludioxonil expected action ppm ppm %activity (Colby) 0.2500 20 0.1250 20 0.0313 0 0.0625 20 0.2500 0.0625 5036 0.1250 0.0625 50 36 0.0313 0.0625 50 20 B2.7: Compound A-1.2Fenpropidin expected action ppm ppm % activity (Colby) 2.0000 70 1.000050 0.5000 20 2.0000 0 1.0000 0 0.5000 0 2.0000 2.0000 100 70 1.00002.0000 70 50 0.5000 2.0000 50 20 0.5000 1.0000 50 20 0.5000 0.5000 50 20

Example B3 Fungicidal Action Against Septoria tritici (Leaf Blotch)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds into a microtiter plate (96-well format)the nutrient broth containing the fungal spores is added. The testplates are incubated at 24° C. and the inhibition of growth is evaluatedafter 4 days. The expected fungicidal action is calculated according tothe Colby method. The results are given in Tables B3:

TABLE B3 Fungicidal action against Septoria tritici: B3.1: CompoundA-1.1 Azoxystrobin expected action ppm ppm % activity (Colby) 0.1250 500.0625 20 0.0625 70 0.1250 0.0625 100 85 0.0625 0.0625 90 76 B3.2:Compound A-1.1 Picoxystrobin expected action ppm ppm % activity (Colby)0.1250 50 0.0625 20 0.0313 70 0.0156 20 0.1250 0.0313 100 85 0.06250.0313 90 76 0.0625 0.0156 50 36 B3.3: Compound A-1.2 Difenoconazoleexpected action ppm ppm % activity (Colby) 0.2500 20 0.0156 0 0.0078 00.0625 90 0.0313 50 0.2500 0.0625 70 92 0.0156 0.0313 70 50 0.00780.0313 70 50 B3.4: Compound A-1.1 Fludioxonil expected action ppm ppm %activity (Colby) 0.5000 90 0.2500 70 0.1250 0 0.0625 0 0.5000 0.1250 10090 0.2500 0.1250 90 70 0.2500 0.0625 90 70 B3.5: Compound A-1.1Cyprodinil expected action ppm ppm % activity (Colby) 0.2500 70 0.125050 2.0000 0 1.0000 0 0.5000 0 0.2500 0 0.1250 0 0.2500 1.0000 100 700.2500 0.5000 90 70 0.2500 0.2500 90 70 0.2500 0.1250 90 70 0.12500.5000 90 50 B3.6: Compound A-1.2 Cyprodinil expected action ppm ppm %activity (Colby) 1.0000 70 0.5000 50 0.2500 20 0.1250 0 2.0000 0 1.00000 0.5000 0 1.0000 2.0000 100 70 1.0000 1.0000 100 70 1.0000 0.5000 90 700.5000 2.0000 100 50 0.5000 1.0000 100 50 0.2500 1.0000 100 20 0.25000.5000 70 20 0.1250 0.5000 70 0 B3.7: Compound A-1.1 Mandipropamidexpected action ppm ppm % activity (Colby) 0.2500 70 0.1250 50 0.5000 00.2500 0 0.1250 0 0.2500 0.5000 90 70 0.2500 0.2500 90 70 0.2500 0.125090 70 0.1250 0.1250 70 50 B3.8: Compound A-1.1 Chlorothalonil expectedaction ppm ppm % activity (Colby) 0.5000 90 0.2500 70 0.1250 50 0.1250 00.0625 0 0.5000 0.1250 100 90 0.2500 0.1250 90 70 0.2500 0.0625 90 700.1250 0.1250 70 50

Example B4 Fungicidal action against Alternaria solani (early blighttomato/potato)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds into a microtiter plate (96-well format)the nutrient broth containing the fungal spores is added. The testplates are incubated at 24° C. and the inhibition of growth is evaluatedafter 3 days.

The expected fungicidal action is calculated according to the Colbymethod. The results are given in Tables B4:

TABLES B4 Fungicidal action against Alternaria solani B4.1: CompoundA-1.1 Azoxystrobin expected action ppm ppm % activity (Colby) 0.2500 500.0625 50 0.0313 20 0.0156 20 0.0078 0 0.2500 50 0.0625 20 0.0313 200.0156 20 0.2500 0.2500 90 75 0.0625 0.0625 70 60 0.0313 0.0625 50 360.0313 0.0313 50 36 0.0313 0.0156 50 36 0.0156 0.0625 50 36 0.01560.0313 50 36 0.0078 0.0313 50 20 B4.2: Compound A-1.2 Azoxystrobinexpected action ppm ppm % activity (Colby) 0.5000 50 0.1250 20 0.0625 00.5000 50 0.2500 50 0.0313 20 0.5000 0.5000 90 75 0.1250 0.5000 70 600.1250 0.0313 50 36 0.0625 0.2500 70 50 0.0625 0.0313 50 20 B4.3:Compound A-1.1 Picoxystrobin expected action ppm ppm % activity (Colby)0.1250 50 0.0625 50 0.0313 20 0.0156 20 0.0078 0 0.0625 50 0.0313 200.0156 20 0.0078 0 0.1250 0.0313 70 60 0.0625 0.0313 70 60 0.0625 0.015670 60 0.0313 0.0625 70 60 0.0313 0.0313 50 36 0.0313 0.0156 50 36 0.03130.0078 50 20 0.0156 0.0313 50 36 0.0078 0.0313 50 20 B4.4: CompoundA-1.2 Picoxystrobin expected action ppm ppm % activity (Colby) 0.5000 500.1250 20 0.0625 0 0.0313 0 2.0000 50 0.5000 50 0.2500 50 0.1250 500.0625 50 0.5000 2.0000 90 75 0.1250 0.5000 70 60 0.1250 0.2500 70 600.0625 0.1250 70 50 0.0625 0.2500 70 50 0.0313 0.1250 70 50 0.03130.0625 70 50 B4.5: Compound A-1.1 Cyproconazole expected action ppm ppm% activity (Colby) 0.2500 50 0.1250 50 0.5000 20 0.2500 0 0.1250 00.2500 0.5000 70 60 0.2500 0.2500 70 50 0.1250 0.2500 70 50 0.12500.1250 70 50 B4.6: Compound A-1.1 Fludioxonil expected action ppm ppm %activity (Colby) 0.2500 50 0.1250 50 0.0625 50 0.0313 20 0.0156 200.2500 50 0.1250 50 0.0625 20 0.0313 0 0.0156 0 0.0078 0 0.2500 0.125090 75 0.2500 0.0625 70 60 0.1250 0.2500 90 75 0.1250 0.0625 70 60 0.12500.0313 70 50 0.0625 0.0625 70 60 0.0313 0.1250 70 60 0.0313 0.0625 70 360.0313 0.0313 50 20 0.0313 0.0156 50 20 0.0313 0.0078 50 20 0.01560.0625 50 36 B4.7: Compound A-1.2 Fludioxonil expected action ppm ppm %activity (Colby) 0.5000 50 0.2500 50 0.1250 20 0.0625 20 0.0313 0 0.500070 0.2500 50 0.1250 20 0.5000 0.2500 90 75 0.5000 0.1250 70 60 0.25000.2500 90 75 0.2500 0.1250 70 60 0.1250 0.5000 90 76 0.1250 0.2500 90 600.1250 0.1250 50 36 0.0625 0.2500 70 60 0.0625 0.1250 50 36 0.03130.1250 50 20 B4.8: Compound A-1.1 Cyprodinil expected action ppm ppm %activity (Colby) 0.2500 50 0.1250 50 0.0625 50 0.2500 50 0.2500 0.250090 75 0.1250 0.2500 90 75 0.0625 0.2500 90 75 B4.9: Compound A-1.1Fenpropidin expected action ppm ppm % activity (Colby) 0.2500 50 0.125050 0.0313 20 1.0000 0 0.5000 0 0.2500 0 0.1250 0 0.2500 1.0000 70 500.2500 0.5000 70 50 0.2500 0.2500 70 50 0.1250 0.5000 70 50 0.03130.1250 50 20

Example B5 Fungicidal Action Against Pseudocercosporella herpotrichoides(Syn. Tapesia yallundae), Eye Spot of Cereals

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds into a microtiter plate (96-well format)the nutrient broth containing the fungal spores is added. The testplates are incubated at 24° C. and the inhibition of growth is evaluatedafter 4 days.

The expected fungicidal action is calculated according to the Colbymethod. The results are given in Tables B5:

TABLES B5 Fungicidal action against Pseudocercosporella hemotrichoides:B5.1: Compound A-1.1 Picoxystrobin expected action ppm ppm % activity(Colby) 0.0625 70 0.0313 50 0.0156 20 0.0078 0 0.2500 50 0.1250 500.0625 50 0.0313 50 0.0156 20 0.0078 0 0.0625 0.2500 100 85 0.06250.1250 100 85 0.0625 0.0156 90 76 0.0313 0.1250 100 75 0.0313 0.0625 9075 0.0313 0.0313 90 75 0.0313 0.0156 70 60 0.0156 0.0625 90 60 0.01560.0313 90 60 0.0156 0.0078 50 20 0.0078 0.0313 70 50 0.0078 0.0156 50 20B5.2: Compound A-1.2 Picoxystrobin expected action ppm ppm % activity(Colby) 0.2500 50 0.1250 20 0.0625 0 0.0313 0 0.0156 0 1.0000 70 0.500050 0.2500 50 0.1250 50 0.0625 50 0.2500 1.0000 100 85 0.2500 0.5000 10075 0.2500 0.2500 90 75 0.2500 0.1250 100 75 0.2500 0.0625 90 75 0.12500.5000 90 60 0.1250 0.2500 90 60 0.1250 0.1250 90 60 0.1250 0.0625 70 600.0625 0.2500 90 50 0.0625 0.1250 90 50 0.0625 0.0625 70 50 0.03130.1250 70 50 0.0313 0.0625 70 50 0.0156 0.0625 70 50 B5.3: CompoundA-1.2 Difenoconazole expected action ppm ppm % activity (Colby) 0.250020 0.1250 0 0.0625 0 0.1250 50 0.2500 0.1250 70 60 0.1250 0.1250 70 500.0625 0.1250 70 50 B5.4: Compound A-1.2 Cyproconazole expected actionppm ppm % activity (Colby) 0.1250 20 0.0625 0 0.2500 70 0.1250 0.2500 9076 0.0625 0.2500 90 70 B5.5: Compound A-1.1 Epoxiconazole expectedaction ppm ppm % activity (Colby) 0.0313 50 0.0156 20 0.1250 70 0.062520 0.0313 0 0.0313 0.1250 100 85 0.0313 0.0625 70 60 0.0156 0.0313 50 200.0156 0.0625 70 36 B5.6: Compound A-1.2 Epoxiconazole expected actionppm ppm % activity (Colby) 0.0625 0 0.0313 0 0.0156 0 0.0078 0 0.0039 00.2500 90 0.1250 70 0.0625 50 0.0313 20 0.0156 0 0.0625 0.2500 100 900.0313 0.1250 100 70 0.0156 0.0625 70 50 0.0078 0.0313 50 20 0.00390.0156 50 0 B5.7: Compound A-1.1 Fludioxonil expected action ppm ppm %activity (Colby) 0.0625 70 Compound A-1.1 Fludioxonil 0.0313 20 0.250020 0.0156 0 0.0078 0 0.0625 0.2500 90 76 0.0625 0.0156 90 70 0.03130.0156 50 20 0.0313 0.0078 50 20 B5.8: Compound A-1.2 Fludioxonilexpected action ppm ppm % activity (Colby) 0.5000 70 0.2500 20 2.0000 201.0000 20 0.5000 20 0.2500 20 0.5000 2.0000 100 76 0.5000 1.0000 100 760.5000 0.5000 90 76 0.2500 1.0000 70 36 0.2500 0.5000 70 36 0.25000.2500 50 36 B5.9: Compound A-1.1 Cyprodinil expected action ppm ppm %activity (Colby) 0.0313 50 0.0156 0 0.0078 0 0.0039 0 0.0313 70 0.015620 0.0313 0.0156 70 60 0.0156 0.0313 90 70 0.0156 0.0156 50 20 0.00780.0156 50 20 0.0039 0.0156 50 20 B5.10: Compound A-1.1 Fenpropidinexpected action ppm ppm % activity (Colby) 0.0625 70 0.0313 50 0.0156 200.2500 0 0.1250 0 0.0625 0 0.0313 0 0.0156 0 0.0625 0.2500 90 70 0.06250.1250 90 70 0.0625 0.0625 90 70 0.0625 0.0313 90 70 0.0625 0.0156 90 700.0313 0.0156 70 50 0.0156 0.0625 50 20 0.0156 0.0313 50 20 B5.11:Compound A-1.1 Chlorothalonil expected action ppm ppm % activity (Colby)0.0313 20 0.0156 20 0.0078 0 0.0313 50 0.0156 0 0.0313 0.0313 70 600.0313 0.0156 50 20 0.0156 0.0313 70 60 0.0078 0.0313 70 50 B5.12:Compound A-1.2 Chlorothalonil expected action ppm ppm % activity (Colby)0.1250 0 0.0625 0 0.0313 0 0.0156 0 0.1250 90 0.0313 50 0.1250 0.1250100 90 0.1250 0.0313 90 50 0.0625 0.1250 100 90 0.0625 0.0313 70 500.0313 0.1250 100 90 0.0313 0.0313 70 50 0.0156 0.0313 70 50

Example B6 Fungicidal action against Pyrenophora teres (Net blotch)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds into a microtiter plate (96-well format)the nutrient broth containing the fungal spores is added. The testplates are incubated at 24° C. and the inhibition of growth is evaluatedafter 4 days. The expected fungicidal action is calculated according tothe Colby method. The results are given in Tables B6:

TABLES B6 Fungicidal action against Pyrenophora feres: B6.1: CompoundA-1.1 Azoxystrobin expected action ppm ppm % activity (Colby) 0.0625 200.0313 20 0.0156 0 0.0078 0 0.1250 70 0.0625 50 0.0313 20 0.0625 0.125090 76 0.0625 0.0313 50 36 0.0313 0.0625 70 60 0.0313 0.0313 50 36 0.01560.0625 70 50 0.0156 0.0313 50 20 0.0313 0.1250 90 76 0.0078 0.0313 50 20B6.2: Compound A-1.2 Azoxystrobin expected action ppm ppm % activity(Colby) 0.2500 20 0.1250 20 0.0313 0 0.0156 0 0.0078 0 0.0625 50 0.031320 0.2500 0.0625 70 60 0.1250 0.0313 50 36 0.0313 0.0625 70 50 0.01560.0625 70 50 0.0156 0.0313 50 20 0.0078 0.0313 50 20 B6.3: CompoundA-1.1 Picoxystrobin expected action ppm ppm % activity (Colby) 0.2500 500.1250 20 0.0625 20 0.0313 20 0.0156 20 0.0625 70 0.0313 50 0.25000.0625 100 85 0.1250 0.0625 100 76 0.1250 0.0313 90 60 0.0625 0.0625 10076 0.0625 0.0313 70 60 0.0313 0.0625 90 76 0.0313 0.0313 70 60 0.01560.0625 90 76 0.0156 0.0313 70 60 B6.4: Compound A-1.1 Difenoconazoleexpected action ppm ppm % activity (Colby) 1.0000 70 0.5000 50 0.2500 500.1250 20 0.0625 20 0.0313 20 0.0156 20 1.0000 70 0.2500 50 0.1250 500.0625 20 1.0000 0.2500 100 85 0.5000 1.0000 100 85 0.5000 0.2500 90 750.5000 0.1250 90 75 0.2500 0.2500 90 75 0.2500 0.1250 90 75 0.25000.0625 70 60 0.1250 0.2500 90 60 0.1250 0.1250 90 60 0.1250 0.0625 70 360.0625 0.2500 70 60 0.0625 0.1250 70 60 0.0625 0.0625 70 36 0.03130.1250 70 60 0.0313 0.0625 50 36 0.0156 0.0625 50 36 B6.5: CompoundA-1.2 Difenoconazole expected action ppm ppm % activity (Colby) 0.250020 0.1250 20 1.0000 70 0.5000 70 0.1250 50 0.0625 20 0.2500 1.0000 90 760.2500 0.5000 90 76 0.2500 0.0625 50 36 0.1250 0.1250 70 60 B6.6:Compound A-1.2 Propiconazole expected action ppm ppm % activity (Colby)1.0000 50 0.5000 50 0.2500 20 2.0000 50 1.0000 20 1.0000 2.0000 90 750.5000 2.0000 90 75 0.5000 1.0000 70 60 0.2500 1.0000 50 36 B6.7:Compound A-1.1 Epoxiconazole expected action ppm ppm % activity (Colby)0.2500 50 0.1250 50 0.0625 20 0.0313 20 0.5000 50 0.2500 20 0.1250 200.2500 0.5000 90 75 0.2500 0.2500 70 60 0.1250 0.5000 90 75 0.12500.2500 70 60 0.0625 0.2500 70 36 0.0625 0.1250 50 36 0.0313 0.1250 70 36B6.8: Compound A-1.2 Epoxiconazole expected action ppm ppm % activity(Colby) 1.0000 50 0.5000 50 0.2500 20 0.1250 20 0.0625 0 1.0000 700.5000 50 0.2500 50 0.1250 20 1.0000 0.5000 90 75 0.5000 0.5000 90 750.2500 1.0000 90 76 0.2500 0.5000 90 60 0.2500 0.2500 70 60 0.25000.1250 50 36 0.1250 0.5000 70 60 0.1250 0.2500 70 60 0.0625 0.2500 70 50B6.9: Compound A-1.1 Fludioxonil expected action ppm ppm % activity(Colby) 0.5000 50 0.2500 50 0.1250 20 0.0625 20 0.0313 20 0.0156 00.1250 70 0.0625 20 0.5000 0.1250 100 85 0.2500 0.1250 100 85 0.12500.1250 100 76 0.1250 0.0625 50 36 0.0625 0.1250 90 76 0.0313 0.1250 9076 0.0313 0.0625 20 36 0.0156 0.0625 90 20 B6.10: Compound A-1.2Fludioxonil expected action ppm ppm % activity (Colby) 0.2500 20 0.125020 0.0625 20 0.0313 0 0.1250 70 0.2500 0.1250 90 76 0.1250 0.1250 90 760.0625 0.1250 90 76 0.0313 0.1250 100 70 B6.11: Compound A-1.2Cyprodinil expected action ppm ppm % activity (Colby) 0.2500 20 0.125020 0.0625 20 0.0313 0 0.2500 50 0.1250 50 0.0625 20 0.0313 20 0.25000.0625 50 36 0.1250 0.0625 50 36 0.1250 0.0313 50 36 0.0625 0.2500 70 600.0625 0.0625 50 36 0.0313 0.1250 70 50 0.0313 0.0625 50 20 B6.12:Compound A-1.1 Fenpropidin expected action ppm ppm % activity (Colby)2.0000 70 0.1250 20 2.0000 0 0.5000 0 0.2500 0 0.1250 0 0.0625 0 2.00002.0000 90 70 0.1250 0.5000 50 20 0.1250 0.2500 50 20 0.1250 0.1250 50 200.1250 0.0625 50 20 B6.13: Compound A-1.1 Mandipropamid expected actionppm ppm % activity (Colby) 0.2500 50 0.1250 20 1.0000 0 0.5000 0 0.25001.0000 70 50 0.1250 0.5000 50 20 B6.14: Compound A-1.1 Chlorothalonilexpected action ppm ppm % activity (Colby) 2.0000 70 1.0000 70 0.5000 700.2500 50 0.1250 20 0.5000 20 2.0000 0.5000 100 76 1.0000 0.5000 100 760.5000 0.5000 100 76 0.2500 0.5000 100 60 0.1250 0.5000 100 36 B6.15:Compound A-1.2 Chlorothalonil expected action ppm ppm % activity (Colby)2.0000 70 1.0000 50 0.5000 50 0.2500 20 0.1250 20 0.5000 20 0.2500 02.0000 0.5000 90 76 1.0000 0.5000 90 60 0.5000 0.5000 100 60 0.25000.5000 100 36 0.2500 0.2500 50 20 0.1250 0.5000 100 36

Example B7 Fungicidal Action Against Gaeumannomyces graminis (Take-allof Cereals)

Mycelial fragments of the fungus from cryogenic storage are directlymixed into nutrient broth (PDB potato dextrose broth). After placing a(DMSO) solution of the test compounds into a microtiter plate (96-wellformat) the nutrient broth containing the fungal spores is added. Thetest plates are incubated at 24 C and the inhibition of growth isevaluated after 4 days. The results are given in Tables B7:

TABLES B7 Fungicidal action against Gaeumannomyces graminis: B7.1:Compound A-1.1 Cyproconazole expected action ppm ppm % activity (Colby)0.0156 50 0.0078 20 0.0625 20 0.0313 0 0.0039 0 0.0156 0.0625 90 600.0156 0.0313 90 50 0.0156 0.0039 90 50 0.0078 0.0039 50 20 B7.2:Compound A-1.1 Difenoconazole expected action ppm ppm % activity (Colby)0.0156 50 0.0625 0 0.0313 0 0.0156 0 0.0039 0 0.0156 0.0625 70 50 0.01560.0313 70 50 0.0156 0.0156 70 50 0.0156 0.0039 90 50 B7.3: CompoundA-1.1 Propiconazole expected action ppm ppm % activity (Colby) 0.0156 700.0625 0 0.0078 0 0.0039 0 0.0156 0.0625 90 70 0.0156 0.0078 90 700.0156 0.0039 90 70 B7.4: Compound A-1.1 Mandipropamid expected actionppm ppm % activity (Colby) 0.0156 70 0.0078 0 0.0625 0 0.0313 0 0.0078 00.0039 0 0.0156 0.0625 90 70 0.0156 0.0313 90 70 0.0156 0.0078 100 700.0078 0.0039 100 0 B7.5: Compound A-1.2 Prothioconazole expected actionppm ppm % activity (Colby) 0.2500 20 0.1250 0 0.0625 0 0.0156 0 0.500090 0.2500 90 0.0625 50 0.2500 0.0625 70 60 0.1250 0.5000 100 90 0.12500.2500 100 90 0.0625 0.2500 100 90 0.0625 0.0625 90 50 0.0156 0.0625 9050 B7.6: Compound A-1.2 Tebuconazole expected action ppm ppm % activity(Colby) 0.2500 20 0.1250 0 0.0313 0 0.1250 50 0.2500 0.1250 90 60 0.12500.1250 70 50 0.0313 0.1250 90 50 B7.7: Compound A-1.2 Fenpropimorphexpected action ppm ppm % activity (Colby) 0.5000 70 Compound A-1.2Fenpropimorph 2.0000 20 1.0000 0 0.5000 0 0.2500 0 0.5000 2.0000 90 760.5000 1.0000 90 70 0.5000 0.5000 90 70 0.5000 0.2500 90 70 B7.8:Compound A-1.2 Fluopyram expected action ppm ppm % activity (Colby)0.5000 90 0.2500 0 2.0000 0 1.0000 0 0.5000 0 0.2500 0 0.1250 0 0.50002.0000 100 90 0.5000 1.0000 100 90 0.5000 0.5000 100 90 0.5000 0.1250100 90 0.2500 0.5000 50 0 0.2500 0.2500 90 0 B7.9: Compound A-1.1Fluopyram expected action ppm ppm % activity (Colby) 0.0156 70 0.0313 00.0156 0 0.0078 0 0.0039 0 0.0156 0.0313 90 70 0.0156 0.0156 100 700.0156 0.0078 90 70 0.0156 0.0039 90 70

Example B8 Fungicidal Action Against Cercospora arachidicola (Syn.Mycosphaerella arachidis), Brown Leaf Spot of Groundnut (Peanut)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds into a microtiter plate (96-well format)the nutrient broth containing the fungal spores is added. The testplates are incubated at 24 C and the inhibition of growth is evaluatedafter 7 days. The results are given in Tables B8:

TABLES B8 Fungicidal action against Cercospora arachidicola: B8.1:Compound A-1.2 Propiconazole expected action ppm ppm % activity (Colby)0.1250 20 0.0313 0 0.1250 90 0.0625 70 0.0313 20 0.0313 0.1250 100 900.0313 0.0625 90 70 0.1250 0.0313 50 36 B8.2: Compound A-1.1Mandipropamid expected action ppm ppm % activity (Colby) 0.0156 200.0078 0 0.0078 0 0.0039 0 0.0156 0.0039 50 20 0.0156 0.0078 50 200.0078 0.0039 70 0 B8.3: Compound A-1.2 Prothioconazole expected actionppm ppm % activity (Colby) 0.0625 0 0.0313 0 0.0156 0 0.0625 70 0.06250.0625 90 70 0.0313 0.0625 90 70 0.0156 0.0625 90 70 B8.4: CompoundA-1.2 Fenpropimorph expected action ppm ppm % activity (Colby) 0.2500 700.1250 20 0.0625 0 0.5000 50 0.2500 20 0.1250 0 0.0625 0 0.2500 0.062590 70 0.1250 0.5000 70 60 0.1250 0.2500 50 36 0.1250 0.1250 50 20 0.25000.2500 90 76 0.1250 0.0625 50 20 0.0625 0.2500 50 20 B8.5: CompoundA-1.1 Bixafen expected action ppm ppm % activity (Colby) 0.0313 700.0156 20 0.0078 0 0.0039 0 0.0313 70 0.0156 20 0.0078 0 0.0039 0 0.03130.0156 90 76 0.0156 0.0313 90 76 0.0156 0.0156 70 36 0.0156 0.0078 50 200.0156 0.0039 50 20 0.0078 0.0156 50 20 0.0039 0.0156 50 20 B8.6:Compound A-1.2 Fluopyram expected action ppm ppm % activity (Colby)0.2500 50 0.1250 20 0.2500 20 0.1250 20 0.0625 0 0.0313 0 0.2500 0.250090 60 0.2500 0.1250 90 60 0.2500 0.0625 90 50 0.1250 0.2500 70 36 0.12500.1250 50 36 0.1250 0.0625 50 20 0.1250 0.0313 70 20

Example B9 Fungicidal Action Against Monographella nivalis (Syn.Microdochium nivale, Fusarium nivale), Snow Mould, Foot Rot of Cereals

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds into a microtiter plate (96-well format)the nutrient broth containing the fungal spores is added. The testplates are incubated at 24 C and the inhibition of growth is evaluatedafter 4 days. The results are given in Tables B9:

TABLES B9 Fungicidal action against Monographella nivalis: B9.1:Compound A-1.1 Fenpropimorph expected action ppm ppm % activity (Colby)0.1250 90 0.0625 50 0.5000 0 0.2500 0 0.1250 0 0.0625 0 0.1250 0.5000100 90 0.1250 0.2500 100 90 0.1250 0.1250 100 90 0.0625 0.2500 70 500.0625 0.1250 70 50 0.0625 0.0625 70 50 B9.2: Compound A-1.2Fenpropimorph expected action ppm ppm % activity (Colby) 2.0000 701.0000 50 2.0000 0 1.0000 0 Compound A-1.2 Fenpropimorph 0.5000 0 2.00002.0000 100 70 2.0000 1.0000 90 70 2.0000 0.5000 90 70 1.0000 2.0000 9050 1.0000 1.0000 70 50 B9.3: Compound A-1.1 Bixafen expected action ppmppm % activity (Colby) 0.0625 50 0.0313 20 0.2500 20 0.1250 0 0.0625 00.0313 0 0.0625 0.2500 90 60 0.0625 0.1250 90 50 0.0625 0.0625 70 500.0625 0.0313 70 50 0.0313 0.1250 50 20 0.0313 0.0625 50 20

Example B10 Fungicidal Action Against Colletotrichum Lacenarium (Syn.Glomerella lagenarium), Anthracnose of Cucurbits

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds into a microtiter plate (96-well format)the nutrient broth containing the fungal spores is added. The testplates are incubated at 24 C and the inhibition of growth is evaluatedafter 3 days. The results are given in Tables B10:

Tables B10 Fungicidal action against Colletotrichum lagenerium: B10.1Compound A-1.2 Fenpropimorph expected action ppm ppm % activity (Colby)1.0000 50 0.5000 20 2.0000 20 1.0000 20 0.5000 0 0.2500 0 1.0000 2.000070 60 1.0000 1.0000 70 60 1.0000 0.5000 70 50 1.0000 0.2500 70 50 0.50002.0000 50 36 B10.2: Compound A-1.2 Ipconazole expected action ppm ppm %activity (Colby) 0.5000 20 0.1250 0 0.0625 0 0.0313 0 0.1250 20 0.50000.1250 50 36 0.1250 0.1250 50 20 0.0625 0.1250 50 20 0.0313 0.1250 50 20

What is claimed is:
 1. A composition suitable for control of diseasescaused by phytopathogens comprising a synergistically effective amountof (A) a compound of formula I

wherein R₁ is difluoromethyl or trifluoromethyl and X is chloro, fluoroor bromo; and (B2) an azole fungicide.
 2. The composition according toclaim 1, wherein component (A) is a compound of formula (I), wherein R₁is difluoromethyl.
 3. The composition according to claim 1, whereincomponent (A) is a compound of formula (I), wherein R₁ is difluoromethyland X is chloro.
 4. The composition according to claim 1, whereincomponent (A) is a compound of formula (I), wherein R₁ is difluoromethyland X is fluoro.
 5. The composition according to claim 1, whereincomponent (A) is a compound of formula (I), wherein R₁ is difluoromethyland X is bromo.
 6. The composition according to claim 1, whereincomponent (B2) is an azole fungicide selected from the group consistingof azaconazole, bromuconazole, cyproconazole, difenoconazole,diniconazole, diniconazole-M, epoxiconazole, fenbuconazole,fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil,imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole,pefurazoate, penconazole, prochloraz, propiconazole, prothioconazole,simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol,triflumizole, triticonazole, diclobutrazol, etaconazole, furconazole,furconazole-cis and quinconazole.
 7. The composition according to claim1, wherein component (B2) is a fungicide selected from the groupconsisting of cyproconazole, difenoconazole, epoxiconazole, flutriafol,ipconazole, metconazole, myclobutanil, penconazole, propiconazole,prothioconazole, tebuconazole, and tetraconazole.
 8. The compositionaccording to claim 1, wherein component (B2) is a fungicide selectedfrom the group consisting of cyproconazole, propiconazole, andtebuconazole.
 9. The composition according to claim 1, wherein component(A) is 3difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(9-dichloromethylidene-benzonorbornene-5-yl) amide and component (B2) isselected from the group consisting of difenoconazole, propiconazole,cyproconazole and epoxiconazole.
 10. The composition according to claim1, wherein component (A) is3difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(9-difluoromethylidene-benzonorbornene-5-yl) amide and component (B2) isselected from the group consisting of difenoconazole, ipconazole,prothioconazole, tebuconazole, propiconazole, cyproconazole, andepoxiconazole.
 11. The composition according to claim 1, wherein theweight ratio of (A) to (B2) is from 2000 : 1 to 1 :
 1000. 12. A methodof controlling diseases on useful plants or on propagation materialthereof caused by phytopathogens, which comprises applying to the usefulplants, the locus thereof or propagation material thereof a compositionaccording to claim
 1. 13. A method of controlling diseases on soybeanplants caused by phytopathogens, which comprises applying to the soybeanplants or to the locus thereof a composition according to claim
 1. 14.The method according to claim 13, wherein the phytopathogen isPhakopsora pachyrhizi.
 15. The method according to claim 13, wherein thesoybean plants are glyphosate tolerant and wherein the compositionfurther comprises glyphosate.
 16. A composition suitable for control ofdiseases caused by phytopathogens comprising a synergistically effectiveamount of (A) a compound of formula I

wherein R₁ is difluoromethyl or trifluoromethyl and X is chloro, fluoroor bromo; and (B2) an azole fungicide selected from the group consistingof cyproconazole, propiconazole, and tebuconazole.
 17. A compositionsuitable for control of diseases caused by phytopathogens comprising asynergistically effective amount of (A) a compound of formula I

wherein component (A) is3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(9-difluoromethylidene-benzonorbornene-5-yl) amide; and (B2) an azolefungicide selected from the group consisting of difenoconazole,tebuconazole, propiconazole, cyproconazole, and epoxiconazole.